JP2010115635A - Photocatalyst dispersion, its method of manufacturing the same and application thereof - Google Patents
Photocatalyst dispersion, its method of manufacturing the same and application thereof Download PDFInfo
- Publication number
- JP2010115635A JP2010115635A JP2009024051A JP2009024051A JP2010115635A JP 2010115635 A JP2010115635 A JP 2010115635A JP 2009024051 A JP2009024051 A JP 2009024051A JP 2009024051 A JP2009024051 A JP 2009024051A JP 2010115635 A JP2010115635 A JP 2010115635A
- Authority
- JP
- Japan
- Prior art keywords
- mass
- oxide particles
- dispersion
- photocatalyst
- tungsten oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000006185 dispersion Substances 0.000 title claims abstract description 454
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 266
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 49
- 239000002245 particle Substances 0.000 claims abstract description 454
- 239000007788 liquid Substances 0.000 claims abstract description 256
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims abstract description 233
- 229910001930 tungsten oxide Inorganic materials 0.000 claims abstract description 233
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 208
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 195
- 239000002612 dispersion medium Substances 0.000 claims abstract description 41
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 75
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 56
- 239000000126 substance Substances 0.000 claims description 52
- 229910052763 palladium Inorganic materials 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 30
- 229910052737 gold Inorganic materials 0.000 claims description 29
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 28
- 150000003839 salts Chemical class 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 54
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 abstract 3
- 238000005189 flocculation Methods 0.000 abstract 1
- 230000016615 flocculation Effects 0.000 abstract 1
- 230000005764 inhibitory process Effects 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 164
- 239000007787 solid Substances 0.000 description 111
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 98
- 239000002253 acid Substances 0.000 description 84
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 66
- 230000001699 photocatalysis Effects 0.000 description 65
- 238000003860 storage Methods 0.000 description 46
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 39
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 38
- 229910052753 mercury Inorganic materials 0.000 description 38
- 239000007864 aqueous solution Substances 0.000 description 33
- 238000006243 chemical reaction Methods 0.000 description 33
- 238000000354 decomposition reaction Methods 0.000 description 31
- 239000010931 gold Substances 0.000 description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 31
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 30
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 26
- 238000003756 stirring Methods 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- 239000000047 product Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000002585 base Substances 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- 241000588724 Escherichia coli Species 0.000 description 8
- 241000191967 Staphylococcus aureus Species 0.000 description 8
- 244000052616 bacterial pathogen Species 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- -1 titanium alkoxide Chemical class 0.000 description 8
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 7
- 239000000654 additive Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 238000004220 aggregation Methods 0.000 description 6
- 230000002776 aggregation Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000010304 firing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 150000003609 titanium compounds Chemical class 0.000 description 6
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 5
- 239000011324 bead Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical class CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000001747 exhibiting effect Effects 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910002094 inorganic tetrachloropalladate Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- HBEQXAKJSGXAIQ-UHFFFAOYSA-N oxopalladium Chemical compound [Pd]=O HBEQXAKJSGXAIQ-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 241000288673 Chiroptera Species 0.000 description 2
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003574 free electron Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910003445 palladium oxide Inorganic materials 0.000 description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 239000004254 Ammonium phosphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 239000005752 Copper oxychloride Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 description 1
- 101100258086 Postia placenta (strain ATCC 44394 / Madison 698-R) STS-01 gene Proteins 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- RAOSIAYCXKBGFE-UHFFFAOYSA-K [Cu+3].[O-]P([O-])([O-])=O Chemical compound [Cu+3].[O-]P([O-])([O-])=O RAOSIAYCXKBGFE-UHFFFAOYSA-K 0.000 description 1
- GMTXBUZKCHNBCH-UHFFFAOYSA-L [K].[Pt](Cl)Cl Chemical compound [K].[Pt](Cl)Cl GMTXBUZKCHNBCH-UHFFFAOYSA-L 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- YKIOKAURTKXMSB-UHFFFAOYSA-N adams's catalyst Chemical compound O=[Pt]=O YKIOKAURTKXMSB-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229920000180 alkyd Polymers 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 1
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical class [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 1
- 235000019289 ammonium phosphates Nutrition 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- FOSZYDNAURUMOT-UHFFFAOYSA-J azane;platinum(4+);tetrachloride Chemical compound N.N.N.N.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] FOSZYDNAURUMOT-UHFFFAOYSA-J 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- HKMOPYJWSFRURD-UHFFFAOYSA-N chloro hypochlorite;copper Chemical compound [Cu].ClOCl HKMOPYJWSFRURD-UHFFFAOYSA-N 0.000 description 1
- XFVGXQSSXWIWIO-UHFFFAOYSA-N chloro hypochlorite;titanium Chemical compound [Ti].ClOCl XFVGXQSSXWIWIO-UHFFFAOYSA-N 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- LLVVIWYEOKVOFV-UHFFFAOYSA-L copper;diiodate Chemical compound [Cu+2].[O-]I(=O)=O.[O-]I(=O)=O LLVVIWYEOKVOFV-UHFFFAOYSA-L 0.000 description 1
- QYCVHILLJSYYBD-UHFFFAOYSA-L copper;oxalate Chemical compound [Cu+2].[O-]C(=O)C([O-])=O QYCVHILLJSYYBD-UHFFFAOYSA-L 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- FWBOFUGDKHMVPI-UHFFFAOYSA-K dicopper;2-oxidopropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[O-]C(=O)CC([O-])(C([O-])=O)CC([O-])=O FWBOFUGDKHMVPI-UHFFFAOYSA-K 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- ATGIETUGWDAYPU-UHFFFAOYSA-M gold monoiodide Chemical compound [Au]I ATGIETUGWDAYPU-UHFFFAOYSA-M 0.000 description 1
- PMCMJPXEJUKOAO-UHFFFAOYSA-M gold(1+);bromide Chemical compound [Au]Br PMCMJPXEJUKOAO-UHFFFAOYSA-M 0.000 description 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 1
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- YWXYYJSYQOXTPL-SLPGGIOYSA-N isosorbide mononitrate Chemical compound [O-][N+](=O)O[C@@H]1CO[C@@H]2[C@@H](O)CO[C@@H]21 YWXYYJSYQOXTPL-SLPGGIOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 229910052622 kaolinite Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NXJCBFBQEVOTOW-UHFFFAOYSA-L palladium(2+);dihydroxide Chemical compound O[Pd]O NXJCBFBQEVOTOW-UHFFFAOYSA-L 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- KGRJUMGAEQQVFK-UHFFFAOYSA-L platinum(2+);dibromide Chemical compound Br[Pt]Br KGRJUMGAEQQVFK-UHFFFAOYSA-L 0.000 description 1
- ZXDJCKVQKCNWEI-UHFFFAOYSA-L platinum(2+);diiodide Chemical compound [I-].[I-].[Pt+2] ZXDJCKVQKCNWEI-UHFFFAOYSA-L 0.000 description 1
- AAIMUHANAAXZIF-UHFFFAOYSA-L platinum(2+);sulfite Chemical compound [Pt+2].[O-]S([O-])=O AAIMUHANAAXZIF-UHFFFAOYSA-L 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000019353 potassium silicate Nutrition 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229940071240 tetrachloroaurate Drugs 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 229910000348 titanium sulfate Inorganic materials 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/687—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/345—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of ultraviolet wave energy
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5025—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with ceramic materials
- C04B41/5041—Titanium oxide or titanates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/106—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20707—Titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20776—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/40—Nitrogen compounds
- B01D2257/406—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/91—Bacteria; Microorganisms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
- C04B2111/00525—Coating or impregnation materials for metallic surfaces
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
- C04B2111/00827—Photocatalysts
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
- C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Physics & Mathematics (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Analytical Chemistry (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Electromagnetism (AREA)
- Optics & Photonics (AREA)
- Plasma & Fusion (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
Description
本発明は、酸化チタン粒子と酸化タングステン粒子とを含有する光触媒体分散液に関する。 The present invention relates to a photocatalyst dispersion liquid containing titanium oxide particles and tungsten oxide particles.
半導体にバンドギャップ以上のエネルギーを持つ光を照射すると、価電子帯の電子が伝導帯に励起され、価電子帯に正孔が、伝導帯に自由電子がそれぞれ生成する。かかる正孔および自由電子は、それぞれ強い酸化力と還元力を有することから、半導体に接触した分子種に酸化還元作用を及ぼす。この酸化還元作用は光触媒作用と呼ばれており、かかる光触媒作用を示し得る半導体は、光触媒体と呼ばれている。このような光触媒体としては、酸化チタン粒子や酸化タングステン粒子などの粒子状のものが知られている。 When a semiconductor is irradiated with light having energy greater than or equal to the band gap, electrons in the valence band are excited to the conduction band, holes are generated in the valence band, and free electrons are generated in the conduction band. Since such holes and free electrons have strong oxidizing power and reducing power, respectively, they exert a redox action on molecular species in contact with the semiconductor. This redox action is called a photocatalytic action, and a semiconductor that can exhibit such a photocatalytic action is called a photocatalyst. As such a photocatalyst, particulates such as titanium oxide particles and tungsten oxide particles are known.
光触媒酸化チタン粒子や光触媒酸化タングステン粒子は、通常、分散媒中に分散させ、光触媒体分散液として光触媒体層の形成に利用されており、例えば、酸化チタン粒子および酸化タングステン粒子を分散媒中に分散させた光触媒体分散液が開示されている（特許文献１）。かかる光触媒体分散液を基材の表面に塗布することにより、基材表面に、酸化チタン粒子および酸化タングステン粒子を含み、光触媒作用を示す光触媒体層を容易に形成することができる。 Photocatalytic titanium oxide particles and photocatalytic tungsten oxide particles are usually dispersed in a dispersion medium and used as a photocatalyst dispersion to form a photocatalyst layer. For example, titanium oxide particles and tungsten oxide particles are dispersed in a dispersion medium. A dispersed photocatalyst dispersion liquid is disclosed (Patent Document 1). By applying such a photocatalyst dispersion liquid to the surface of the substrate, a photocatalyst layer that includes titanium oxide particles and tungsten oxide particles and exhibits a photocatalytic action can be easily formed on the surface of the substrate.
しかしながら、酸化チタン粒子および酸化タングステン粒子を分散媒中に分散させた従来の光触媒体分散液は、粒子が互いに凝集して固液分離し易いという欠点があった。例えば、光触媒体分散液を輸送、保管する間に該分散液中の粒子が凝集して固液分離が生じると、分散液を基材に塗布するなどして光触媒体層を形成する際に、良好な膜を形成することができず、その結果、充分な光触媒活性を付与できない、といった問題を招くことになる。 However, the conventional photocatalyst dispersion liquid in which titanium oxide particles and tungsten oxide particles are dispersed in a dispersion medium has a drawback that the particles are aggregated with each other and are easily solid-liquid separated. For example, when the photocatalyst dispersion liquid is transported and stored, particles in the dispersion agglomerate and solid-liquid separation occurs, and when the photocatalyst layer is formed by applying the dispersion to a substrate, A good film cannot be formed, and as a result, a problem that sufficient photocatalytic activity cannot be imparted is caused.
そこで、本発明の課題は、粒子の凝集が抑制されて固液分離を起こしにくい光触媒体分散液を提供することにある。 Accordingly, an object of the present invention is to provide a photocatalyst dispersion liquid in which aggregation of particles is suppressed and solid-liquid separation hardly occurs.
本発明者らは、上記課題を解決するべく鋭意研究を重ねた。その結果、酸化チタン粒子および酸化タングステン粒子を分散媒中に分散させた分散液において、酸化チタン粒子に対して特定量のリン酸（塩）を共存させると、粒子の凝集が抑制されることを見出した。さらに、その際、リン酸（塩）は酸化チタン粒子近傍に存在させることが、粒子の凝集を抑制するうえで有効であり、そのように酸化チタン粒子近傍にリン酸（塩）が存在する分散液を得るには、酸化チタン粒子と酸化タングステン粒子との混合に先立ち、リン酸（塩）溶液中に酸化チタン粒子を分散させておけばよいことを見出した。本発明は、これらの知見に基づき完成したものである。 The present inventors have intensively studied to solve the above problems. As a result, in a dispersion liquid in which titanium oxide particles and tungsten oxide particles are dispersed in a dispersion medium, coagulation of particles is suppressed when a specific amount of phosphoric acid (salt) is allowed to coexist with titanium oxide particles. I found it. Further, in this case, it is effective to suppress phosphoric acid (salt) in the vicinity of the titanium oxide particles in order to suppress the aggregation of the particles. It has been found that in order to obtain a liquid, titanium oxide particles may be dispersed in a phosphoric acid (salt) solution prior to mixing of titanium oxide particles and tungsten oxide particles. The present invention has been completed based on these findings.
すなわち、本発明の光触媒体分散液は、酸化チタン粒子、酸化タングステン粒子、リン酸（塩）および分散媒を含み、前記リン酸（塩）の含有量が、前記酸化チタン粒子に対して０．００１〜０．２モル倍であることを特徴とする。
本発明の光触媒体分散液の製造方法は、リン酸（塩）を溶解させた分散媒中に酸化チタン粒子を分散させ、得られた酸化チタン粒子分散液と酸化タングステン粒子とを混合することを特徴とする。
本発明の光触媒機能製品は、表面に光触媒体層を備える光触媒機能製品であって、前記光触媒体層が前記本発明の光触媒体分散液を用いて形成されていることを特徴とする。
That is, the photocatalyst dispersion liquid of the present invention contains titanium oxide particles, tungsten oxide particles, phosphoric acid (salt) and a dispersion medium, and the phosphoric acid (salt) content is 0. 0 relative to the titanium oxide particles. It is characterized by being 001 to 0.2 mole times.
The method for producing a photocatalyst dispersion liquid of the present invention comprises dispersing titanium oxide particles in a dispersion medium in which phosphoric acid (salt) is dissolved, and mixing the obtained titanium oxide particle dispersion liquid and tungsten oxide particles. Features.
The photocatalyst functional product of the present invention is a photocatalyst functional product having a photocatalyst layer on the surface, wherein the photocatalyst layer is formed using the photocatalyst dispersion liquid of the present invention.
本発明によれば、粒子の凝集が抑制されて固液分離を起こしにくい光触媒体分散液を提供することができる。そして、この光触媒体分散液を用いれば、高い光触媒活性を示す光触媒体層を容易に形成することが可能になる。 According to the present invention, it is possible to provide a photocatalyst dispersion liquid in which aggregation of particles is suppressed and solid-liquid separation hardly occurs. If this photocatalyst dispersion liquid is used, a photocatalyst layer exhibiting high photocatalytic activity can be easily formed.
（光触媒体分散液）
本発明の光触媒体分散液は、酸化チタン粒子、酸化タングステン粒子、リン酸（塩）および分散媒を含むものである。つまり、本発明の光触媒体分散液は、光触媒作用を有する光触媒体である酸化チタン粒子および酸化タングステン粒子が、リン酸（塩）の存在下で分散媒中に分散したものである。このとき、酸化チタン粒子近傍に存在しているリン酸（塩）は、酸化チタン粒子の表面に吸着した状態になる。この状態の酸化チタン粒子が酸化タングステン粒子と凝集しにくいため、本発明の光触媒体分散液は、粒子の凝集が抑制されたものとなるのである。なお、リン酸（塩）が酸化チタン粒子近傍に存在した光触媒体分散液は、例えば、後述する本発明の光触媒体分散液の製造方法により容易に得られる。
(Photocatalyst dispersion)
The photocatalyst dispersion liquid of the present invention contains titanium oxide particles, tungsten oxide particles, phosphoric acid (salt) and a dispersion medium. That is, the photocatalyst dispersion liquid of the present invention is obtained by dispersing titanium oxide particles and tungsten oxide particles, which are photocatalysts having photocatalytic activity, in a dispersion medium in the presence of phosphoric acid (salt). At this time, phosphoric acid (salt) existing in the vicinity of the titanium oxide particles is adsorbed on the surface of the titanium oxide particles. Since the titanium oxide particles in this state are less likely to aggregate with the tungsten oxide particles, the photocatalyst dispersion liquid of the present invention is one in which particle aggregation is suppressed. In addition, the photocatalyst dispersion liquid in which phosphoric acid (salt) is present in the vicinity of the titanium oxide particles can be easily obtained by, for example, the method for producing the photocatalyst dispersion liquid of the present invention described later.
本発明の光触媒体分散液を構成する酸化チタン粒子は、光触媒作用を示す粒子状の酸化チタンであれば、特に制限はされないが、例えば、メタチタン酸粒子、結晶型がアナターゼ型、ブルッカイト型、ルチル型などである二酸化チタン〔ＴｉＯ2〕粒子等が挙げられる。なお、酸化チタン粒子は、単独で用いてもよいし、２種以上を併用してもよい。 The titanium oxide particles constituting the photocatalyst dispersion liquid of the present invention are not particularly limited as long as they are particulate titanium oxide exhibiting a photocatalytic action. For example, metatitanic acid particles, crystal type is anatase type, brookite type, rutile Examples thereof include titanium dioxide [TiO2] particles which are molds. In addition, a titanium oxide particle may be used independently and may use 2 or more types together.
メタチタン酸粒子は、例えば、硫酸チタニルの水溶液を加熱して加水分解させる方法により得ることができる。
二酸化チタン粒子は、例えば、（ｉ）硫酸チタニルまたは塩化チタンの水溶液を加熱することなく、これに塩基を加えることにより沈殿物を得、得られた沈殿物を焼成する方法、（ｉｉ）チタンアルコキシドに水、酸の水溶液または塩基の水溶液を加えて沈殿物を得、得られた沈殿物を焼成する方法、（ｉｉｉ）メタチタン酸を焼成する方法、などによって得ることができる。これらの方法で得られる二酸化チタン粒子は、焼成する際の焼成温度や焼成時間を調整することにより、アナターゼ型、ブルッカイト型、ルチル型など、所望の結晶型にすることができる。
Metatitanic acid particles can be obtained, for example, by a method in which an aqueous solution of titanyl sulfate is heated and hydrolyzed.
The titanium dioxide particles can be obtained, for example, by (i) a method in which a base is added to this solution without heating an aqueous solution of titanyl sulfate or titanium chloride to obtain a precipitate, and the obtained precipitate is calcined, (ii) titanium alkoxide It is possible to obtain a precipitate by adding water, an aqueous solution of an acid or an aqueous solution of a base to the precipitate, and (iii) a method of baking metatitanic acid, or the like. The titanium dioxide particles obtained by these methods can be made into a desired crystal type such as anatase type, brookite type or rutile type by adjusting the baking temperature and baking time when baking.
また、本発明の光触媒体分散液を構成する酸化チタン粒子は、チタン化合物と塩基とを反応させ、得られた生成物にアンモニアを添加し、熟成した後、固液分離し、固形分を焼成する方法などでも得られる。この方法では、チタン化合物として、例えば、三塩化チタン〔ＴｉＣｌ3〕、四塩化チタン〔ＴｉＣｌ4〕、硫酸チタン〔Ｔｉ（ＳＯ4）2・ｍＨ2Ｏ、０≦ｍ≦２０〕、オキシ硫酸チタン〔ＴｉＯＳＯ4・ｎＨ2Ｏ、０≦ｎ≦２０〕、オキシ塩化チタン〔ＴｉＯＣｌ2〕等を用いることができる。チタン化合物と反応させる塩基としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸カリウム、アンモニア、ヒドラジン、ヒドロキシルアミン、モノエタノールアミン、非環式アミン化合物、環式脂肪族アミン化合物等を用いることができる。 The titanium oxide particles constituting the photocatalyst dispersion liquid of the present invention are obtained by reacting a titanium compound and a base, adding ammonia to the obtained product, aging, solid-liquid separation, and firing the solid content It can also be obtained by a method such as In this method, examples of titanium compounds include titanium trichloride [TiCl 3 ], titanium tetrachloride [TiCl 4 ], titanium sulfate [Ti (SO 4 ) 2 .mH 2 O, 0 ≦ m ≦ 20], and titanium oxysulfate. [TiOSO 4 · nH 2 O, 0 ≦ n ≦ 20], titanium oxychloride [TiOCl 2 ], or the like can be used. Examples of the base to be reacted with the titanium compound include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia, hydrazine, hydroxylamine, monoethanolamine, acyclic amine compound, and cyclic aliphatic amine compound. Can be used.
チタン化合物と塩基との反応は、ｐＨ２以上、好ましくはｐＨ３以上であり、ｐＨ７以下、好ましくはｐＨ５以下である範囲で行われる。また、そのときの反応温度は、通常９０℃以下、好ましくは７０℃以下、さらに好ましくは５５℃以下である。チタン化合物と塩基との反応は、得られる酸化チタンの粉砕性を向上させるために、過酸化水素存在下で行ってもよい。熟成は、例えば、アンモニアが添加された生成物を攪拌しながら、０℃以上、好ましくは１０℃以上であり、１１０℃以下、好ましくは８０℃以下、より好ましくは５５℃以下である温度範囲に、１分以上、好ましくは１０分以上であり、１０時間以内、好ましくは２時間以内の範囲で保持することにより行うことができる。反応および熟成に用いられる塩基（アンモニア）の総量は、水の存在下でチタン化合物を水酸化チタンに変えるのに必要な塩基の化学量論量を超える量であればよいが、塩基の量が多いほど、可視光照射によって高い光触媒活性を示す光触媒体となるので、通常１．１モル倍以上、さらに好ましくは１．５モル倍以上である。一方、塩基の量があまり多くなっても、量に見合った効果は得られないので、その上限は、２０モル倍以下、さらには１０モル倍以下が適当である。 The reaction between the titanium compound and the base is carried out in the range of pH 2 or higher, preferably pH 3 or higher, pH 7 or lower, preferably pH 5 or lower. Moreover, the reaction temperature at that time is 90 degrees C or less normally, Preferably it is 70 degrees C or less, More preferably, it is 55 degrees C or less. The reaction between the titanium compound and the base may be performed in the presence of hydrogen peroxide in order to improve the grindability of the resulting titanium oxide. Aging is, for example, in a temperature range of 0 ° C. or higher, preferably 10 ° C. or higher, 110 ° C. or lower, preferably 80 ° C. or lower, more preferably 55 ° C. or lower while stirring the product to which ammonia has been added. It is 1 minute or more, preferably 10 minutes or more, and it can be carried out by holding within a range of 10 hours or less, preferably 2 hours or less. The total amount of base (ammonia) used for the reaction and ripening may be an amount that exceeds the stoichiometric amount of the base required to convert the titanium compound to titanium hydroxide in the presence of water. The larger the amount, the higher the photocatalytic activity that shows high photocatalytic activity by irradiation with visible light. On the other hand, even if the amount of the base is too large, an effect commensurate with the amount cannot be obtained. Therefore, the upper limit is suitably 20 mol times or less, and more preferably 10 mol times or less.
熟成された生成物の固液分離は、加圧濾過、減圧濾過、遠心分離、デカンテーションなどで行うことができる。固液分離では、得られる固形分を洗浄する操作をあわせて行うことが好ましい。固液分離された固形分の焼成は、気流焼成炉、トンネル炉、回転炉などを用いて、通常２５０℃以上、好ましくは２７０℃以上であり、６００℃以下、好ましくは５００℃以下、より好ましくは４００℃以下の温度範囲で行うことができる。焼成時間は、焼成温度や焼成装置の種類により異なるが、通常１０分以上、好ましくは３０分以上であり、３０時間以内、好ましくは５時間以内である。なお、焼成して得られる酸化チタンには、必要に応じて、タングステン、ニオブ、鉄、ニッケルの酸化物や水酸化物などのような固体酸性を示す化合物や、ランタン、セリウム、カルシウムの酸化物や水酸化物などのような固体塩基性を示す化合物や、インジウム酸化物、ビスマス酸化物のような可視光線を吸収する金属化合物等を担持させてもよい。 Solid-liquid separation of the aged product can be performed by pressure filtration, vacuum filtration, centrifugation, decantation, or the like. In the solid-liquid separation, it is preferable to perform an operation for washing the obtained solid content. The solid-liquid separation of the solid-liquid separated is usually performed at 250 ° C. or higher, preferably 270 ° C. or higher, and 600 ° C. or lower, preferably 500 ° C. or lower, using an airflow firing furnace, tunnel furnace, rotary furnace, or the like. Can be performed in a temperature range of 400 ° C. or lower. The firing time varies depending on the firing temperature and the type of firing apparatus, but is usually 10 minutes or longer, preferably 30 minutes or longer, within 30 hours, preferably within 5 hours. In addition, the titanium oxide obtained by firing includes, if necessary, a compound showing solid acidity such as an oxide or hydroxide of tungsten, niobium, iron, nickel, or an oxide of lanthanum, cerium, or calcium. Alternatively, a compound having solid basicity such as a hydroxide or a metal compound that absorbs visible light such as indium oxide or bismuth oxide may be supported.
本発明の光触媒体分散液を構成する酸化チタン粒子としては、上記の他にも、特開２００１−７２４１９号公報、特開２００１−１９０９５３号公報、特開２００１−３１６１１６号公報、特開２００１−３２２８１６号公報、特開２００２−２９７４９号公報、特開２００２−９７０１９号公報、ＷＯ０１／１０５５２パンフレット、特開２００１−２１２４５７公報、特開２００２−２３９３９５号公報）、ＷＯ０３／０８０２４４パンフレット、ＷＯ０２／０５３５０１パンフレット、特開２００７−６９０９３号公報、Chemistry Letters, Vol.32, No.2, P.196-197(2003)、Chemistry Letters, Vol.32, No.4, P.364-365(2003)、Chemistry Letters, Vol.32, No.8, P.772-773(2003)、Chem. Mater., 17, P.1548-1552(2005)等に記載の酸化チタン粒子を用いてもよい。また、特開２００１−２７８６２５号公報、特開２００１−２７８６２６号公報、特開２００１−２７８６２７号公報、特開２００１−３０２２４１号公報、特開２００１−３３５３２１号公報、特開２００１−３５４４２２号公報、特開２００２−２９７５０号公報、特開２００２−４７０１２号公報、特開２００２−６０２２１号公報、特開２００２−１９３６１８号公報、特開２００２−２４９３１９号公報などに記載の方法により得られる酸化チタン粒子を用いることもできる。 In addition to the above, the titanium oxide particles constituting the photocatalyst dispersion liquid of the present invention include JP-A-2001-72419, JP-A-2001-190953, JP-A-2001-316116, JP-A-2001-2001. 322816, JP2002-29749, JP200297019, WO01 / 10552 pamphlet, JP2001-212457, JP2002239395), WO03 / 080244 pamphlet, WO02 / 053501 pamphlet. JP 2007-69093 A, Chemistry Letters, Vol. 32, No. 2, P.196-197 (2003), Chemistry Letters, Vol. 32, No. 4, P.364-365 (2003), Chemistry Titanium oxide particles described in Letters, Vol. 32, No. 8, P. 772-773 (2003), Chem. Mater., 17, P. 1548-1552 (2005), etc. may be used. JP 2001-278625 A, JP 2001-278626 A, JP 2001-278627 A, JP 2001-302241 A, JP 2001-335321 A, JP 2001-354422 A, Titanium oxide particles obtained by the methods described in JP 2002-29750 A, JP 2002-47012 A, JP 2002-60221 A, JP 2002-193618 A, JP 2002-249319 A, etc. Can also be used.
前記酸化チタン粒子の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常２０〜１５０ｎｍ、好ましくは４０〜１００ｎｍである。
前記酸化チタン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常１００〜５００ｍ2／ｇ、好ましくは３００〜４００ｍ2／ｇである。
The particle diameter of the titanium oxide particles is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 20 to 150 nm, preferably 40 to 100 nm.
BET specific surface area of the titanium oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, usually 100 to 500 m 2 / g, preferably from 300~400m 2 / g.
本発明の光触媒体分散液を構成する酸化タングステン粒子は、光触媒作用を示す粒子状の酸化タングステンであれば、特に制限はされないが、例えば、三酸化タングステン〔ＷＯ3〕粒子等が挙げられる。なお、酸化タングステン粒子は、単独で用いてもよいし、２種以上を併用してもよい。 The tungsten oxide particles constituting the photocatalyst dispersion liquid of the present invention are not particularly limited as long as they are particulate tungsten oxide exhibiting a photocatalytic action, and examples thereof include tungsten trioxide [WO 3 ] particles. The tungsten oxide particles may be used alone or in combination of two or more.
三酸化タングステン粒子は、例えば、（ｉ）タングステン酸塩の水溶液に酸を加えることにより、沈殿物としてタングステン酸を得、得られたタングステン酸を焼成する方法、（ｉｉ）メタタングステン酸アンモニウム、パラタングステン酸アンモニウムを加熱することにより熱分解する方法、などによって得ることができる。 The tungsten trioxide particles are obtained by, for example, (i) a method in which tungstic acid is obtained as a precipitate by adding an acid to an aqueous solution of tungstate, and the obtained tungstic acid is fired. (Ii) ammonium metatungstate, para It can be obtained by a method of thermally decomposing by heating ammonium tungstate.
前記酸化タングステン粒子の粒子径は、特に制限されないが、光触媒作用の観点からは、平均分散粒子径で、通常５０〜２００ｎｍ、好ましくは８０〜１３０ｎｍである。
前記酸化タングステン粒子のＢＥＴ比表面積は、特に制限されないが、光触媒作用の観点からは、通常５〜１００ｍ2／ｇ、好ましくは２０〜５０ｍ2／ｇである。
The particle diameter of the tungsten oxide particles is not particularly limited, but from the viewpoint of photocatalysis, the average dispersed particle diameter is usually 50 to 200 nm, preferably 80 to 130 nm.
BET specific surface area of the tungsten oxide particles is not particularly limited, from the viewpoint of photocatalytic activity, typically 5 to 100 m 2 / g, preferably from 20 to 50 m 2 / g.
本発明の光触媒体分散液において、前記酸化チタン粒子と前記酸化タングステン粒子との比率（酸化チタン粒子：酸化タングステン粒子）は、質量比で、通常４：１〜１：８、好ましくは２：３〜３：２である。 In the photocatalyst dispersion liquid of the present invention, the ratio of the titanium oxide particles to the tungsten oxide particles (titanium oxide particles: tungsten oxide particles) is usually 4: 1 to 1: 8, preferably 2: 3 in mass ratio. ~ 3: 2.
本発明の光触媒体分散液を構成するリン酸（塩）としては、リン酸、もしくはそのアンモニウム塩、ナトリウム塩、カリウム塩等が挙げられるが、これらの中でも特に、リン酸二水素アンモニウム、リン酸水素二アンモニウム等のリン酸アンモニウム塩が好ましい。なお、リン酸（塩）は、単独で用いてもよいし、２種以上を併用してもよい。 Examples of the phosphoric acid (salt) constituting the photocatalyst dispersion liquid of the present invention include phosphoric acid or its ammonium salt, sodium salt, potassium salt and the like. Among these, ammonium dihydrogen phosphate, phosphoric acid, among others. Ammonium phosphate salts such as diammonium hydrogen are preferred. In addition, phosphoric acid (salt) may be used independently and may use 2 or more types together.
本発明の光触媒体分散液においては、前記リン酸（塩）の含有量は、前記酸化チタン粒子に対して０．００１〜０．２モル倍である。好ましくは、０．０１モル倍以上、０．１モル倍以下である。リン酸（塩）の含有量が０．００１モル倍未満であると、分散液中の粒子の凝集を充分に抑制することができず、一方、０．２モル倍を超えて用いても、その量に見合っただけのさらなる効果は得られないので、経済的に不利となる。 In the photocatalyst dispersion liquid of the present invention, the phosphoric acid (salt) content is 0.001 to 0.2 mole times the titanium oxide particles. Preferably, they are 0.01 mol times or more and 0.1 mol times or less. When the content of phosphoric acid (salt) is less than 0.001 mol times, aggregation of particles in the dispersion cannot be sufficiently suppressed. Since no further effect corresponding to the amount is obtained, it is economically disadvantageous.
本発明の光触媒体分散液を構成する分散媒は、前記リン酸（塩）を溶解する溶媒であれば特に制限はなく、通常、水を主成分とする水性溶媒が用いられる。具体的には、分散媒は、水単独であってもよいし、水と水溶性有機溶媒との混合溶媒であってもよい。水と水溶性有機溶媒との混合溶媒を用いる場合には、水の含有量が５０質量％以上であることが好ましい。水溶性有機溶媒としては、例えば、メタノール、エタノール、プロパノール、ブタノールなどの水溶性アルコール溶媒、アセトン、メチルエチルケトン等が挙げられる。なお、分散媒は、単独で用いてもよいし、２種以上を併用してもよい。 The dispersion medium constituting the photocatalyst dispersion liquid of the present invention is not particularly limited as long as it is a solvent that dissolves the phosphoric acid (salt), and an aqueous solvent mainly containing water is usually used. Specifically, the dispersion medium may be water alone or a mixed solvent of water and a water-soluble organic solvent. When a mixed solvent of water and a water-soluble organic solvent is used, the content of water is preferably 50% by mass or more. Examples of the water-soluble organic solvent include water-soluble alcohol solvents such as methanol, ethanol, propanol, and butanol, acetone, and methyl ethyl ketone. In addition, a dispersion medium may be used independently and may use 2 or more types together.
前記分散媒の含有量は、酸化チタン粒子および酸化タングステン粒子の合計量に対して、通常５〜２００質量倍、好ましくは１０〜１００質量倍である。分散媒が５質量倍未満であると、酸化チタン粒子および酸化タングステン粒子が沈降し易くなり、一方、２００質量倍を超えると、容積効率の点で不利となるので、いずれも好ましくない。 The content of the dispersion medium is usually 5 to 200 times by mass, preferably 10 to 100 times by mass with respect to the total amount of titanium oxide particles and tungsten oxide particles. If the dispersion medium is less than 5 mass times, the titanium oxide particles and the tungsten oxide particles are liable to settle, whereas if it exceeds 200 mass times, it is disadvantageous in terms of volumetric efficiency.
本発明の光触媒体分散液は、電子吸引性物質またはその前駆体をも含有することが好ましい。電子吸引性物質とは、光触媒体（すなわち、酸化チタン粒子および酸化タングステン粒子）の表面に担持されて電子吸引性を発揮しうる化合物であり、電子吸引性物質の前駆体とは、光触媒体の表面で電子吸引性物質に遷移しうる化合物（例えば、光照射により電子吸引性物質に還元されうる化合物）である。電子吸引性物質が光触媒体の表面に担持されて存在すると、光の照射により伝導帯に励起された電子と価電子帯に生成した正孔との再結合が抑制され、光触媒作用をより高めることができる。 The photocatalyst dispersion liquid of the present invention preferably contains an electron-withdrawing substance or a precursor thereof. An electron-withdrawing substance is a compound that can be carried on the surface of a photocatalyst (that is, titanium oxide particles and tungsten oxide particles) and can exhibit electron-withdrawing properties. A compound that can transition to an electron-withdrawing substance on the surface (for example, a compound that can be reduced to an electron-withdrawing substance by light irradiation). When an electron-withdrawing substance is supported on the surface of the photocatalyst, recombination of electrons excited in the conduction band by light irradiation and holes generated in the valence band is suppressed, and the photocatalytic action is further enhanced. Can do.
前記電子吸引性物質またはその前駆体は、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ、Ａｇ、Ｆｅ、Ｎｂ、Ｒｕ、Ｉｒ、ＲｈおよびＣｏからなる群より選ばれる１種以上の金属原子を含有してなるものであることが好ましい。より好ましくは、Ｃｕ、Ｐｔ、ＡｕおよびＰｄのうちの１種以上の金属原子を含有してなるものである。例えば、前記電子吸引性物質としては、前記金属原子からなる金属、もしくは、これらの金属の酸化物や水酸化物等が挙げられ、電子吸引性物質の前駆体としては、前記金属原子からなる金属の硝酸塩、硫酸塩、ハロゲン化物、有機酸塩、炭酸塩、りん酸塩等が挙げられる。 The electron withdrawing substance or its precursor contains one or more metal atoms selected from the group consisting of Cu, Pt, Au, Pd, Ag, Fe, Nb, Ru, Ir, Rh and Co. It is preferable that More preferably, it contains one or more metal atoms of Cu, Pt, Au and Pd. For example, the electron-withdrawing substance may be a metal made of the metal atom, or an oxide or hydroxide of these metals, and the precursor of the electron-withdrawing substance may be a metal made of the metal atom. Nitrates, sulfates, halides, organic acid salts, carbonates, phosphates, and the like.
電子吸引性物質の好ましい具体例としては、Ｃｕ、Ｐｔ、Ａｕ、Ｐｄ等の金属が挙げられる。また、電子吸引性物質の前駆体の好ましい具体例としては、Ｃｕを含む前駆体として、硝酸銅〔Ｃｕ(ＮＯ3)2〕、硫酸銅〔ＣｕＳＯ4〕、塩化銅〔ＣｕＣｌ2、ＣｕＣｌ〕、臭化銅〔ＣｕＢｒ2、ＣｕＢｒ〕、沃化銅〔ＣｕＩ〕、沃素酸銅〔ＣｕＩ2Ｏ6〕、塩化アンモニウム銅〔Ｃｕ(ＮＨ4) 2Ｃｌ4〕、オキシ塩化銅〔Ｃｕ2Ｃｌ(ＯＨ) 3〕、酢酸銅〔ＣＨ3ＣＯＯＣｕ、(ＣＨ3ＣＯＯ) 2Ｃｕ〕、蟻酸銅〔(ＨＣＯＯ) 2Ｃｕ〕、炭酸銅〔ＣｕＣＯ3）、蓚酸銅〔ＣｕＣ2Ｏ4〕、クエン酸銅〔Ｃｕ2Ｃ6Ｈ4Ｏ7〕、リン酸銅〔ＣｕＰＯ4〕等が；Ｐｔを含む前駆体として、塩化白金〔ＰｔＣｌ2、ＰｔＣｌ4〕、臭化白金〔ＰｔＢｒ2、ＰｔＢｒ4〕、沃化白金〔ＰｔＩ2、ＰｔＩ4〕、塩化白金カリウム〔Ｋ2(ＰｔＣｌ4)〕、ヘキサクロロ白金酸〔Ｈ2ＰｔＣｌ6〕、亜硫酸白金〔Ｈ3Ｐｔ(ＳＯ3) 2ＯＨ〕、酸化白金〔ＰｔＯ2〕、塩化テトラアンミン白金〔Ｐｔ(ＮＨ3) 4Ｃｌ2〕、炭酸水素テトラアンミン白金〔Ｃ2Ｈ14Ｎ4Ｏ6Ｐｔ〕、テトラアンミン白金リン酸水素〔Ｐｔ(ＮＨ3) 4ＨＰＯ4〕、水酸化テトラアンミン白金〔Ｐｔ(ＮＨ3) 4(ＯＨ) 2〕、硝酸テトラアンミン白金〔Ｐｔ(ＮＯ3) 2(ＮＨ3) 4〕、テトラアンミン白金テトラクロロ白金〔(Ｐｔ(ＮＨ3) 4)(ＰｔＣｌ4)〕等が；Ａｕを含む前駆体として、塩化金〔ＡｕＣｌ〕、臭化金〔ＡｕＢｒ〕、沃化金〔ＡｕＩ〕、水酸化金〔Ａｕ(ＯＨ) 2〕、テトラクロロ金酸〔ＨＡｕＣｌ4〕、テトラクロロ金酸カリウム〔ＫＡｕＣｌ4〕、テトラブロモ金酸カリウム〔ＫＡｕＢｒ4〕、酸化金〔Ａｕ2Ｏ3〕等が；Ｐｄを含む前駆体として、例えば、酢酸パラジウム〔(ＣＨ3ＣＯＯ) 2Ｐｄ〕、塩化パラジウム〔ＰｄＣｌ2〕、臭化パラジウム〔ＰｄＢｒ2〕、沃化パラジウム〔ＰｄＩ2〕、水酸化パラジウム〔Ｐｄ(ＯＨ) 2〕、硝酸パラジウム〔Ｐｄ(ＮＯ3) 2〕、酸化パラジウム〔ＰｄＯ〕、硫酸パラジウム〔ＰｄＳＯ4〕、テトラクロロパラジウム酸カリウム〔Ｋ2(ＰｄＣｌ4)〕、テトラブロモパラジウム酸カリウム〔Ｋ2(ＰｄＢｒ4)〕、テトラアンミンパラジウム塩化物〔Ｐｄ(ＮＨ3)4Ｃｌ2〕、テトラアンミンパラジウム臭化物〔Ｐｄ(ＮＨ3)4Ｂｒ2〕、テトラアンミンパラジウム硝酸塩〔Ｐｄ(ＮＨ3)4(ＮＯ3)2〕、テトラアンミンパラジウムテトラクロロパラジウム酸〔(Ｐｄ(ＮＨ3)4)(ＰｄＣｌ4）〕、テトラクロロパラジウム酸アンモニウム〔(ＮＨ4)2ＰｄＣｌ4〕等が；それぞれ挙げられる。なお、電子吸引性物質またはその前駆体は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。また、１種以上の電子吸引性物質と１種以上の前駆体とを併用してもよいことは勿論である。 Preferable specific examples of the electron withdrawing substance include metals such as Cu, Pt, Au, and Pd. Moreover, as a preferable specific example of the precursor of an electron withdrawing substance, as a precursor containing Cu, copper nitrate [Cu (NO 3 ) 2 ], copper sulfate [CuSO 4 ], copper chloride [CuCl 2 , CuCl], Copper bromide [CuBr 2 , CuBr], copper iodide [CuI], copper iodate [CuI 2 O 6 ], ammonium chloride [Cu (NH 4 ) 2 Cl 4 ], copper oxychloride [Cu 2 Cl (OH) ) 3 ], copper acetate [CH 3 COOCu, (CH 3 COO) 2 Cu], copper formate [(HCOO) 2 Cu], copper carbonate [CuCO 3 ), copper oxalate [CuC 2 O 4 ], copper citrate [ Cu 2 C 6 H 4 O 7 ], copper phosphate [CuPO 4 ], etc .; as precursors containing Pt, platinum chloride [PtCl 2 , PtCl 4 ], platinum bromide [PtBr 2 , PtBr 4 ], iodide platinum [PtI 2, PtI 4], potassium platinum chloride [K 2 (PtCl 4)], hexose Chloroplatinic acid [H 2 PtCl 6], platinum sulfite [H 3 Pt (SO 3) 2 OH ], platinum oxide [PtO 2], tetraammine platinum chloride [Pt (NH 3) 4 Cl 2], bicarbonate tetraammineplatinum [ C 2 H 14 N 4 O 6 Pt], tetraammineplatinum hydrogen phosphate [Pt (NH 3 ) 4 HPO 4 ], tetraammineplatinum platinum [Pt (NH 3 ) 4 (OH) 2 ], tetraammineplatinum nitrate [Pt ( NO 3 ) 2 (NH 3 ) 4 ], tetraammineplatinum tetrachloroplatinum [(Pt (NH 3 ) 4 ) (PtCl 4 )] and the like; as a precursor containing Au, gold chloride [AuCl], gold bromide [ AuBr], gold iodide [AuI], gold hydroxide [Au (OH) 2 ], tetrachloroauric acid [HAuCl 4 ], potassium tetrachloroaurate [KAuCl 4 ], potassium tetrabromoaurate [KAuBr 4 ], oxidation Gold [Au 2 O 3 ] etc. As precursors containing Pd, for example, palladium acetate [(CH 3 COO) 2 Pd], palladium chloride [PdCl 2 ], palladium bromide [PdBr 2 ], palladium iodide [PdI 2 ], palladium hydroxide [ Pd (OH) 2 ], palladium nitrate [Pd (NO 3 ) 2 ], palladium oxide [PdO], palladium sulfate [PdSO 4 ], potassium tetrachloropalladate [K 2 (PdCl 4 )], potassium tetrabromopalladate [K 2 (PdBr 4 )], tetraammine palladium chloride [Pd (NH 3 ) 4 Cl 2 ], tetraammine palladium bromide [Pd (NH 3 ) 4 Br 2 ], tetraammine palladium nitrate [Pd (NH 3 ) 4 (NO 3) 2], tetraammine palladium tetrachloropalladate [(Pd (NH 3) 4) (PdCl 4) ], tetrachloropalladate Ammonium [(NH 4) 2 PdCl 4] and the like are; like, respectively. In addition, an electron withdrawing substance or its precursor may each be used independently, and may use 2 or more types together. Needless to say, one or more electron-withdrawing substances and one or more precursors may be used in combination.
前記電子吸引性物質またはその前駆体をも含有させる場合、その含有量は、金属原子換算で、酸化チタン粒子および酸化タングステン粒子の合計量１００質量部に対して、通常０．００５〜０．６質量部、好ましくは０．０１〜０．４質量部である。電子吸引性物質またはその前駆体が０．００５質量部未満であると、電子吸引性物質による光触媒活性の向上効果が充分に得られないおそれがあり、一方、０．６質量部を超えると、却って光触媒作用が低下するおそれがある。 When the electron-withdrawing substance or its precursor is also contained, the content is usually 0.005 to 0.6 with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of metal atoms. Part by mass, preferably 0.01 to 0.4 part by mass. If the electron-withdrawing substance or its precursor is less than 0.005 parts by mass, the effect of improving the photocatalytic activity by the electron-withdrawing substance may not be sufficiently obtained, while if it exceeds 0.6 parts by mass, On the contrary, the photocatalytic action may be reduced.
本発明の光触媒体分散液は、本発明の効果を損なわない範囲で、従来公知の各種添加剤を含んでいてもよい。なお、添加剤は、それぞれ単独で用いてもよいし、２種以上を併用してもよい。 The photocatalyst dispersion liquid of the present invention may contain conventionally known various additives as long as the effects of the present invention are not impaired. In addition, an additive may each be used independently and may use 2 or more types together.
前記添加剤としては、例えば、光触媒作用を向上させる目的で添加されるものが挙げられる。このような光触媒作用向上効果を目的とした添加剤としては、具体的には、非晶質シリカ、シリカゾル、水ガラス、オルガノポリシロキサンなどの珪素化合物；非晶質アルミナ、アルミナゾル、水酸化アルミニウムなどのアルミニウム化合物；ゼオライト、カオリナイトのようなアルミノ珪酸塩；酸化マグネシウム、酸化カルシウム、酸化ストロンチウム、酸化バリウム、水酸化マグネシウム、水酸化カルシウム、水酸化ストロンチウム、水酸化バリウムなどのアルカリ土類金属酸化物またはアルカリ度類金属水酸化物；リン酸カルシウム、モレキュラーシーブ、活性炭、有機ポリシロキサン化合物の重縮合物、リン酸塩、フッ素系ポリマー、シリコン系ポリマー、アクリル樹脂、ポリエステル樹脂、メラミン樹脂、ウレタン樹脂、アルキド樹脂；等が挙げられる。
さらに、前記添加剤としては、光触媒体分散液を基材表面に塗布した際に光触媒体（酸化チタン粒子および酸化タングステン粒子）をより強固に基材の表面に保持させるためのバインダー等を用いることもできる（例えば、特開平８−６７８３５号公報、特開平９−２５４３７号公報、特開平１０−１８３０６１号公報、特開平１０−１８３０６２号公報、特開平１０−１６８３４９号公報、特開平１０−２２５６５８号公報、特開平１１−１６２０号公報、特開平１１−１６６１号公報、特開２００４−０５９６８６号公報、特開２００４−１０７３８１号公報、特開２００４−２５６５９０号公報、特開２００４−３５９９０２号公報、特開２００５−１１３０２８号公報、特開２００５−２３０６６１号公報、特開２００７−１６１８２４号公報など参照）。
Examples of the additive include those added for the purpose of improving the photocatalytic action. Specific examples of such additives for improving the photocatalytic effect include silicon compounds such as amorphous silica, silica sol, water glass, and organopolysiloxane; amorphous alumina, alumina sol, aluminum hydroxide, and the like. Aluminosilicates such as zeolite and kaolinite; alkaline earth metal oxides such as magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide Or alkali metal hydroxides: calcium phosphate, molecular sieve, activated carbon, polycondensate of organic polysiloxane compound, phosphate, fluoropolymer, silicone polymer, acrylic resin, polyester resin, melamine resin, urethane resin, alkyd Fats; and the like.
Further, as the additive, a binder for holding the photocatalyst (titanium oxide particles and tungsten oxide particles) more firmly on the surface of the substrate when the photocatalyst dispersion liquid is applied to the surface of the substrate is used. (For example, JP-A-8-67835, JP-A-9-25437, JP-A-10-183061, JP-A-10-183062, JP-A-10-168349, JP-A-10-225658. Publication No. 11-1620, No. 11-1661, No. 2004-059686, No. 2004-107381, No. 2004-256590, No. 2004-359902. JP, 2005-113028, JP, 2005-230661, JP, 2007-1618. See, for 4 JP).
本発明の光触媒体分散液は、その水素イオン濃度が、通常ｐＨ２．０〜ｐＨ７．０、好ましくはｐＨ３．０〜ｐＨ６．０である。水素イオン濃度がｐＨ２．０未満であると、酸性が強すぎて取扱いが面倒であり、一方、ｐＨ７．０を超えると、酸化タングステン粒子が溶解するおそれがあるので、いずれも好ましくない。光触媒体分散液の水素イオン濃度は、通常、酸を加えることにより調整すればよい。水素イオン濃度の調整に用いることのできる酸としては、例えば、硝酸、塩酸、硫酸、リン酸、ギ酸、酢酸、蓚酸等が挙げられる。 The hydrogen ion concentration of the photocatalyst dispersion liquid of the present invention is usually pH 2.0 to pH 7.0, preferably pH 3.0 to pH 6.0. When the hydrogen ion concentration is less than pH 2.0, the acidity is too strong and the handling is troublesome. On the other hand, when the pH exceeds 7.0, the tungsten oxide particles may be dissolved. The hydrogen ion concentration of the photocatalyst dispersion liquid may be usually adjusted by adding an acid. Examples of the acid that can be used for adjusting the hydrogen ion concentration include nitric acid, hydrochloric acid, sulfuric acid, phosphoric acid, formic acid, acetic acid, oxalic acid, and the like.
（光触媒体分散液の製造方法）
本発明の光触媒体分散液の製造方法は、リン酸（塩）を溶解させた分散媒中に酸化チタン粒子を分散させ、得られた酸化チタン粒子分散液と酸化タングステン粒子とを混合するものである。このように、酸化チタン粒子を、酸化タングステン粒子と混合する前にあらかじめリン酸（塩）を溶解させた分散媒に分散させておくことにより、酸化チタン粒子の表面はリン酸（塩）が吸着した状態となる。この状態の酸化チタン粒子は酸化タングステン粒子と凝集しにくいため、本発明の製造方法により得られた光触媒体分散液は、粒子の凝集が抑制されたものとなる。
(Method for producing photocatalyst dispersion)
The method for producing a photocatalyst dispersion liquid of the present invention comprises dispersing titanium oxide particles in a dispersion medium in which phosphoric acid (salt) is dissolved, and mixing the obtained titanium oxide particle dispersion liquid and tungsten oxide particles. is there. As described above, by dispersing the titanium oxide particles in a dispersion medium in which phosphoric acid (salt) is dissolved in advance before mixing with the tungsten oxide particles, phosphoric acid (salt) is adsorbed on the surface of the titanium oxide particles. It will be in the state. Since the titanium oxide particles in this state are difficult to aggregate with the tungsten oxide particles, the photocatalyst dispersion liquid obtained by the production method of the present invention is one in which particle aggregation is suppressed.
リン酸（塩）を溶解させた分散媒中に酸化チタン粒子を分散させて酸化チタン粒子分散液を得る際には、両者を混合した後さらに分散処理を施すことが好ましい。分散処理には、例えば、媒体撹拌式分散機を用いるなど、従来公知の方法を採用することができる。なお、酸化チタン粒子を分散させるリン酸（塩）含有分散媒を調製するに際しては、リン酸（塩）の使用量は（光触媒体分散液）の項で前述したリン酸（塩）の含有量の範囲とすればよい。 When titanium oxide particles are dispersed in a dispersion medium in which phosphoric acid (salt) is dissolved to obtain a titanium oxide particle dispersion, it is preferable to perform a dispersion treatment after mixing the two. For the dispersion treatment, a conventionally known method can be employed, for example, using a medium stirring type disperser. In preparing a phosphoric acid (salt) -containing dispersion medium in which titanium oxide particles are dispersed, the amount of phosphoric acid (salt) used is the phosphoric acid (salt) content described above in the section of (photocatalyst dispersion). It may be in the range.
前記酸化タングステン粒子は、そのまま前記酸化チタン粒子分散液に混合してもよいが、分散媒中に分散させて酸化タングステン粒子分散液としたのちに前記酸化チタン粒子分散液と混合することが好ましい。酸化タングステン粒子を分散媒に分散させる際には、両者を混合した後さらに分散処理を施すことが好ましい。分散処理には、例えば、媒体撹拌式分散機を用いるなど、従来公知の方法を採用することができる。
なお、酸化チタン粒子分散液と酸化タングステン粒子分散液とを混合する場合、両分散液に用いる分散媒の種類は、混合後の分散媒が（光触媒体分散液）の項で前述した分散媒の通りとなる限り、同じであってもよいし、異なっていてもよい。また、両分散液における分散媒の使用量も、最終的に得られる光触媒体分散液における分散媒の含有量が（光触媒体分散液）の項で前述した通りとなる範囲であれば、特に制限されない。
The tungsten oxide particles may be mixed with the titanium oxide particle dispersion as it is. However, it is preferable that the tungsten oxide particles are dispersed in a dispersion medium to form a tungsten oxide particle dispersion and then mixed with the titanium oxide particle dispersion. When dispersing the tungsten oxide particles in the dispersion medium, it is preferable to further disperse them after mixing them. For the dispersion treatment, a conventionally known method can be employed, for example, using a medium stirring type disperser.
When mixing the titanium oxide particle dispersion and the tungsten oxide particle dispersion, the type of the dispersion medium used for both dispersions is the same as that of the dispersion medium described above in the section (Photocatalyst dispersion). As long as it becomes a street, it may be the same or different. Also, the amount of the dispersion medium used in both dispersions is not particularly limited as long as the content of the dispersion medium in the finally obtained photocatalyst dispersion liquid is in the range described above in the section of (photocatalyst dispersion liquid). Not.
酸化チタン粒子分散液と酸化タングステン粒子とを混合するに際しては、両者の使用量は、酸化チタン粒子と酸化タングステン粒子との比率が（光触媒体分散液）の項で前述した範囲となるようにすればよい。 When mixing the titanium oxide particle dispersion and the tungsten oxide particles, the amount of both used should be such that the ratio of the titanium oxide particles to the tungsten oxide particles is in the range described above in the section of (photocatalyst dispersion). That's fine.
本発明の光触媒体分散液の製造方法は、電子吸引性物質またはその前駆体を添加する工程を含むことが好ましい。ここで、電子吸引性物質またはその前駆体の添加は、前記酸化チタン粒子分散液に対して行ってもよいし、前記酸化タングステン粒子分散液に対して行ってもよいし、前記酸化チタン粒子分散液と前記酸化タングステン粒子分散液もしくは酸化タングステン粒子とを混合した後の分散液に対して行ってもよいが、高い光触媒活性を得る観点からは、電子吸引性物質またはその前駆体は前記酸化タングステン粒子分散液に添加するのが好ましい。
なお、電子吸引性物質またはその前駆体を添加する場合、その添加量は、最終的に得られる光触媒体分散液における電子吸引性物質またはその前駆体の含有量が（光触媒体分散液）の項で前述した範囲となるようにすればよい。
The method for producing a photocatalyst dispersion liquid of the present invention preferably includes a step of adding an electron withdrawing substance or a precursor thereof. Here, the addition of the electron withdrawing substance or the precursor thereof may be performed on the titanium oxide particle dispersion, the tungsten oxide particle dispersion, or the titanium oxide particle dispersion. However, from the standpoint of obtaining high photocatalytic activity, the electron-withdrawing substance or its precursor is the tungsten oxide. It is preferable to add to the particle dispersion.
In addition, when adding an electron withdrawing substance or its precursor, the addition amount is the term of the content of the electron withdrawing substance or its precursor in the finally obtained photocatalyst dispersion liquid (photocatalyst dispersion liquid). In this case, the range may be set as described above.
前記電子吸引性物質の前駆体を添加した場合には、その添加後に光照射を行うことが好ましい。照射する光としては、特に制限はなく、可視光線でもよいし、紫外線でもよい。光照射を行うことにより、光励起によって生成した電子によって前駆体が還元されて電子吸引性物質となり、光触媒体粒子（酸化チタン粒子および酸化タングステン粒子）の表面に担持される。なお、前記前駆体を添加した場合に、たとえ光照射を行なわなくても、得られた光触媒体分散液により形成された光触媒体層に光が照射された時点で電子吸引性物質へ変換されることになるので、その光触媒能が損なわれることはない。 When the precursor of the electron-withdrawing substance is added, it is preferable to perform light irradiation after the addition. There is no restriction | limiting in particular as light to irradiate, Visible light may be sufficient and an ultraviolet-ray may be sufficient. By performing light irradiation, the precursor is reduced by electrons generated by photoexcitation to become an electron-withdrawing substance, and is supported on the surface of the photocatalyst particles (titanium oxide particles and tungsten oxide particles). When the precursor is added, the photocatalyst layer formed from the obtained photocatalyst dispersion liquid is converted into an electron-withdrawing substance when light is irradiated to the photocatalyst layer formed by the obtained photocatalyst dispersion liquid. As a result, the photocatalytic ability is not impaired.
前記光照射は、前記前駆体の添加後であれば、どの段階で行なってもよいが、好ましくは、酸化チタン粒子分散液と酸化タングステン粒子との混合前に行なうのがよい。
また、前記電子吸引性物質の前駆体を添加した場合には、より効率よく電子吸引性物質を得る目的で、光照射の前に、本発明効果を損なわない範囲で、適宜、メタノールやエタノールや蓚酸等を加えることもできる。
The light irradiation may be performed at any stage as long as it is after the addition of the precursor, but is preferably performed before mixing the titanium oxide particle dispersion and the tungsten oxide particles.
In addition, when the electron-withdrawing substance precursor is added, for the purpose of obtaining the electron-withdrawing substance more efficiently, methanol, ethanol, Succinic acid or the like can also be added.
なお、本発明の光触媒体分散液の製造方法においては、（光触媒体分散液）の項で前述した各種添加剤を添加することもできる。その場合、それら添加剤の添加はどの段階で行なってもよいが、例えば、酸化チタン粒子分散液と酸化タングステン粒子分散液もしくは酸化タングステン粒子との混合後に行なうことが好ましい。 In the method for producing a photocatalyst dispersion liquid of the present invention, various additives described above in the section of (photocatalyst dispersion liquid) can also be added. In that case, the addition of these additives may be performed at any stage, but for example, it is preferably performed after mixing the titanium oxide particle dispersion and the tungsten oxide particle dispersion or the tungsten oxide particles.
（光触媒機能製品）
本発明の光触媒機能製品は、前記本発明の光触媒体分散液を用いて形成された光触媒体層を表面に備えるものである。ここで、光触媒体層は、光触媒作用を示す光触媒体、すなわち酸化チタン粒子および酸化タングステン粒子からなる。そして、本発明の光触媒体分散液が電子吸引性物質またはその前駆体を含む場合には、当該電子吸引性物質またはその前駆体は、酸化チタン粒子および酸化タングステン粒子の表面に担持される。なお、担持された前駆体は、例えば光が照射されることなどによって、電子吸引性物質に遷移する。
(Photocatalytic functional products)
The photocatalyst functional product of the present invention is provided with a photocatalyst layer formed on the surface using the photocatalyst dispersion liquid of the present invention. Here, the photocatalyst layer is composed of a photocatalyst exhibiting a photocatalytic action, that is, titanium oxide particles and tungsten oxide particles. And when the photocatalyst body dispersion liquid of this invention contains an electron withdrawing substance or its precursor, the said electron withdrawing substance or its precursor is carry | supported on the surface of a titanium oxide particle and a tungsten oxide particle. The supported precursor transitions to an electron-withdrawing substance, for example, when irradiated with light.
前記光触媒体層は、例えば、本発明の光触媒体分散液を基材（製品）の表面に塗布した後、分散媒を揮発させるなど、従来公知の成膜方法によって形成することができる。光触媒体層の膜厚は、特に制限されるものではなく、通常、その用途等に応じて、数百ｎｍ〜数ｍｍまで適宜設定すればよい。光触媒体層は、基材（製品）の内表面または外表面であれば、どの部分に形成されていてもよいが、例えば、光（可視光線）が照射される面であって、かつ悪臭物質が発生する箇所と連続または断続して空間的につながる面に形成されていることが好ましい。なお、基材（製品）の材質は、形成される光触媒体層を実用に耐えうる強度で保持できる限り、特に制限されるものではなく、例えば、プラスチック、金属、セラミックス、木材、コンクリート、紙など、あらゆる材料からなる製品を対象にすることができる。 The photocatalyst layer can be formed by a conventionally known film formation method, for example, after applying the photocatalyst dispersion of the present invention to the surface of a substrate (product) and volatilizing the dispersion medium. The film thickness of the photocatalyst body layer is not particularly limited, and usually may be appropriately set from several hundred nm to several mm according to the application. The photocatalyst layer may be formed on any part as long as it is an inner surface or an outer surface of the base material (product). For example, the photocatalyst layer is a surface irradiated with light (visible light), and a malodorous substance. It is preferably formed on a surface that is continuously or intermittently connected to a place where the occurrence occurs. The material of the base material (product) is not particularly limited as long as the formed photocatalyst layer can be held at a strength that can be practically used. For example, plastic, metal, ceramics, wood, concrete, paper, etc. , Products made of any material can be targeted.
本発明の光触媒機能製品の具体例としては、例えば、天井材、タイル、ガラス、壁紙、壁材、床等の建築資材、自動車内装材（自動車用インストルメントパネル、自動車用シート、自動車用天井材）、冷蔵庫やエアコン等の家電製品、衣類やカーテン等の繊維製品などが挙げられる。 Specific examples of the photocatalytic functional product of the present invention include, for example, building materials such as ceiling materials, tiles, glass, wallpaper, wall materials, floors, automobile interior materials (automobile instrument panels, automotive seats, automotive ceiling materials, etc. ), Home appliances such as refrigerators and air conditioners, and textile products such as clothes and curtains.
本発明の光触媒機能製品は、屋外においては勿論のこと、蛍光灯やナトリウムランプのような可視光源からの光しか受けない屋内環境においても、光照射によって高い触媒作用を示す。したがって、本発明の光触媒体分散液を、例えば病院の天井材、タイル、ガラスなどに塗布して乾燥させると、屋内照明による光照射によって、ホルムアルデヒドやアセトアルデヒドなどの揮発性有機物、アルデヒド類、メルカプタン類、アンモニアなどの悪臭物質、窒素酸化物の濃度を低減させ、さらには黄色ブドウ球菌や大腸菌等の病原菌等を分解、除去することができる。 The photocatalytic functional product of the present invention exhibits a high catalytic action by light irradiation not only outdoors but also in an indoor environment receiving only light from a visible light source such as a fluorescent lamp and a sodium lamp. Therefore, when the photocatalyst dispersion liquid of the present invention is applied to, for example, hospital ceiling materials, tiles, and glass, and dried, volatile organic substances such as formaldehyde and acetaldehyde, aldehydes, and mercaptans are obtained by light irradiation by indoor lighting. In addition, the concentration of malodorous substances such as ammonia and nitrogen oxides can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be decomposed and removed.
以下、本発明を実施例によって詳細に説明するが、本発明はこれらに限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these.
なお、実施例および比較例における各物性の測定およびその光触媒活性の評価については、以下の方法で行った。 In addition, about the measurement of each physical property in an Example and a comparative example, and the evaluation of the photocatalytic activity, it performed with the following method.
＜結晶型＞
Ｘ線回折装置（リガク社製「ＲＩＮＴ２０００／ＰＣ」）を用いてＸ線回折スペクトルを測定し、そのスペクトルから結晶型を決定した。
<Crystal type>
An X-ray diffraction spectrum was measured using an X-ray diffractometer (“RINT2000 / PC” manufactured by Rigaku Corporation), and a crystal type was determined from the spectrum.
＜ＢＥＴ比表面積＞
比表面積測定装置（湯浅アイオニクス社製「モノソーブ」）を用いて窒素吸着法により測定した。
<BET specific surface area>
It measured by the nitrogen adsorption method using the specific surface area measuring apparatus ("Monosorb" by Yuasa Ionics Co., Ltd.).
＜平均分散粒子径＞
サブミクロン粒度分布測定装置（コールター社製「Ｎ４Ｐｌｕｓ」）を用いて粒度分布を測定し、この装置に付属のソフトにより自動的に単分散モード解析して得られた結果を、平均分散粒子径（ｎｍ）とした。
<Average dispersed particle size>
The particle size distribution was measured using a sub-micron particle size distribution measuring device (“N4Plus” manufactured by Coulter, Inc.), and the result obtained by performing the monodisperse mode analysis automatically with the software attached to this device was used as the average dispersed particle size nm).
＜光触媒活性の評価：アセトアルデヒドの分解＞
光触媒活性は、蛍光灯の光の照射下でのアセトアルデヒドの分解反応における一次反応速度定数を測定することにより評価した。
まず、光触媒活性測定用の試料を作製した。すなわち、ガラス製シャーレ（外径７０ｍｍ、内径６６ｍｍ、高さ１４ｍｍ、容量約４８ｍＬ）に、得られた光触媒体分散液を、底面の単位面積あたりの固形分換算の滴下量が１ｇ／ｍ2となるように滴下し、シャーレの底面全体に均一となるように展開した。次いで、このシャーレを１１０℃の乾燥機内で大気中１時間保持することにより乾燥させて、ガラス製シャーレの底面に光触媒体層を形成した。この光触媒体層に、紫外線強度が２ｍＷ／ｃｍ2となるようにブラックライトからの紫外線を１６時間照射して、これを光触媒活性測定用試料とした。
<Evaluation of photocatalytic activity: decomposition of acetaldehyde>
The photocatalytic activity was evaluated by measuring a first-order reaction rate constant in the decomposition reaction of acetaldehyde under irradiation of light from a fluorescent lamp.
First, a sample for measuring photocatalytic activity was prepared. That is, in a glass petri dish (outer diameter: 70 mm, inner diameter: 66 mm, height: 14 mm, capacity: about 48 mL), the obtained photocatalyst dispersion liquid has a dripping amount in terms of solid content per unit area of the bottom surface of 1 g / m 2 . It dripped so that it might become, and it developed so that it might become uniform to the whole bottom face of a petri dish. Next, this petri dish was dried by holding it in the air at 110 ° C. for 1 hour in the atmosphere to form a photocatalyst layer on the bottom of the glass petri dish. This photocatalyst layer was irradiated with ultraviolet light from a black light for 16 hours so that the ultraviolet intensity was 2 mW / cm 2, and this was used as a sample for photocatalytic activity measurement.
次に、この光触媒活性測定用試料をシャーレごとガスバッグ（内容積３Ｌ）の中に入れて密閉し、次いで、このガスバッグ内を真空にした後、酸素と窒素との体積比が１：４である混合ガス１．８Ｌを封入し、さらにその中に１容量％でアセトアルデヒドを含む窒素ガス９ｍＬを封入して、暗所で室温下１時間保持した。その後、市販の白色蛍光灯を光源とし、測定用試料近傍での照度が１０００ルクス（ミノルタ社製照度計「Ｔ−１０」で測定）となるようにガスバッグの外から蛍光灯の光を照射し、アセトアルデヒドの分解反応を行った。このとき、測定試料近傍の紫外光の強度は６．５μＷ／ｃｍ2（トプコン社製紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定）であった。蛍光灯の光照射を開始してから１．５時間毎にガスバッグ内のガスをサンプリングし、アセトアルデヒドの濃度をガスクロマトグラフ（島津製作所社製「ＧＣ−１４Ａ」）にて測定した。そして、照射時間に対するアセトアルデヒドの残存濃度から一次反応速度定数を算出し、これをアセトアルデヒド分解能として評価した。この一次反応速度定数が大きいほど、アセトアルデヒドの分解能（すなわち光触媒活性）が高いと言える。 Next, the sample for photocatalytic activity measurement was put together with the petri dish in a gas bag (internal volume 3 L) and sealed, and then the inside of the gas bag was evacuated, and the volume ratio of oxygen to nitrogen was 1: 4. Was mixed with 1.8 L of mixed gas, and 9 mL of nitrogen gas containing acetaldehyde at 1 vol% was sealed therein, and the mixture was kept in the dark at room temperature for 1 hour. After that, using a commercially available white fluorescent lamp as the light source, irradiate the fluorescent lamp light from the outside of the gas bag so that the illuminance near the measurement sample is 1000 lux (measured with the illuminometer “T-10” manufactured by Minolta) Then, the decomposition reaction of acetaldehyde was performed. At this time, the intensity of the ultraviolet light in the vicinity of the measurement sample was 6.5 μW / cm 2 (measured by attaching a light receiving unit “UD-36” manufactured by the company to a UV intensity meter “UVR-2” manufactured by Topcon Corporation). The gas in the gas bag was sampled every 1.5 hours after the light irradiation of the fluorescent lamp was started, and the concentration of acetaldehyde was measured with a gas chromatograph (“GC-14A” manufactured by Shimadzu Corporation). Then, a first-order reaction rate constant was calculated from the residual concentration of acetaldehyde with respect to the irradiation time, and this was evaluated as acetaldehyde resolution. It can be said that the higher the first-order reaction rate constant is, the higher the resolution (that is, photocatalytic activity) of acetaldehyde is.
＜光触媒活性の評価：ホルムアルデヒドの分解＞
光触媒活性は、蛍光灯の光の照射下でのホルムアルデヒドの分解反応における一次反応速度定数を測定することにより評価した。
まず、光触媒活性測定用の試料を作製した。すなわち、ガラス製シャーレ（外径７０ｍｍ、内径６６ｍｍ、高さ１４ｍｍ、容量約４８ｍＬ）に、得られた光触媒体分散液を、底面の単位面積あたりの固形分換算の滴下量が１ｇ／ｍ2となるように滴下し、シャーレの底面全体に均一となるように展開した。次いで、このシャーレを１１０℃の乾燥機内で大気中１時間保持することにより乾燥させて、ガラス製シャーレの底面に光触媒体層を形成した。この光触媒体層に、紫外線強度が２ｍＷ／ｃｍ2となるようにブラックライトからの紫外線を１６時間照射して、これを光触媒活性測定用試料とした。
<Evaluation of photocatalytic activity: decomposition of formaldehyde>
The photocatalytic activity was evaluated by measuring the first-order rate constant in the decomposition reaction of formaldehyde under the irradiation of light from a fluorescent lamp.
First, a sample for measuring photocatalytic activity was prepared. That is, in a glass petri dish (outer diameter: 70 mm, inner diameter: 66 mm, height: 14 mm, capacity: about 48 mL), the obtained photocatalyst dispersion liquid has a dripping amount in terms of solid content per unit area of the bottom surface of 1 g / m 2 . It dripped so that it might become, and it developed so that it might become uniform to the whole bottom face of a petri dish. Next, this petri dish was dried by holding it in the air at 110 ° C. for 1 hour in the atmosphere to form a photocatalyst layer on the bottom of the glass petri dish. This photocatalyst layer was irradiated with ultraviolet light from a black light for 16 hours so that the ultraviolet intensity was 2 mW / cm 2, and this was used as a sample for photocatalytic activity measurement.
次に、この光触媒活性測定用試料をシャーレごとガスバッグ（内容積１Ｌ）の中に入れて密閉し、次いで、このガスバッグ内を真空にした後、酸素を０．１２L封入し、さらにその中に濃度１００ｐｐｍでホルムアルデヒドを含む窒素ガス０．４８Ｌを封入して、暗所で室温下４５分間保持した。その後、市販の白色蛍光灯を光源とし、測定用試料近傍での照度が６０００ルクス（ミノルタ社製照度計「Ｔ−１０」で測定）となるようにガスバッグの外から蛍光灯の光を照射し、ホルムアルデヒドの分解反応を行った。このとき、測定試料近傍の紫外光の強度は４０μＷ／ｃｍ2（トプコン社製紫外線強度計「ＵＶＲ−２」に、同社製受光部「ＵＤ−３６」を取り付けて測定）であった。蛍光灯の光照射を開始してから１５分毎にガスバッグ内のガスをサンプリングし、ホルムアルデヒドの濃度をガスクロマトグラフ（アジレントテクノロジー社製「Ａｇｉｌｅｎｔ３０００マイクロＧＣ」）にて測定した。そして、照射時間に対するホルムアルデヒドの残存濃度から一次反応速度定数を算出し、これをホルムアルデヒド分解能として評価した。この一次反応速度定数が大きいほど、ホルムアルデヒドの分解能（すなわち光触媒活性）が高いと言える。 Next, the sample for measuring photocatalytic activity is put in a gas bag (internal volume 1 L) together with the petri dish, and then the inside of the gas bag is evacuated, and then 0.12 L of oxygen is sealed therein, and further, Was filled with 0.48 L of nitrogen gas containing formaldehyde at a concentration of 100 ppm, and kept in the dark at room temperature for 45 minutes. Then, using a commercially available white fluorescent lamp as the light source, irradiate the fluorescent lamp from the outside of the gas bag so that the illuminance in the vicinity of the measurement sample is 6000 lux (measured with the illuminometer “T-10” manufactured by Minolta). Then, decomposition reaction of formaldehyde was performed. At this time, the intensity of the ultraviolet light in the vicinity of the measurement sample was 40 μW / cm 2 (measured by attaching the UV receiver “UD-36” manufactured by the company to the UV intensity meter “UVR-2” manufactured by Topcon Corporation). The gas in the gas bag was sampled every 15 minutes after the light irradiation of the fluorescent lamp was started, and the concentration of formaldehyde was measured with a gas chromatograph (“Agilent 3000 Micro GC” manufactured by Agilent Technologies). Then, a first-order reaction rate constant was calculated from the remaining concentration of formaldehyde with respect to the irradiation time, and this was evaluated as formaldehyde resolution. It can be said that the larger the first-order reaction rate constant, the higher the formaldehyde resolution (ie, photocatalytic activity).
（製造例１−酸化チタン粒子分散液の調製）
ｐＨ電極と、このｐＨ電極に接続され、２５質量％アンモニア水を供給してｐＨを一定に調整する機構を有するｐＨコントローラーとを備えた反応容器（すなわち、この反応容器では、容器内の液のｐＨが設定値より低くなると、アンモニア水が供給されはじめ、ｐＨが設定値になるまで連続供給される）に、イオン交換水３０ｋｇを入れ、ｐＨコントローラーの設定値をｐＨ４とした。他方、オキシ硫酸チタン７５ｋｇをイオン交換水５０ｋｇに溶解させた後、得られた水溶液に冷却下で３５％過酸化水素水３０ｋｇを添加して、混合溶液を調製した。この混合溶液を、上記反応容器内を４２ｒｐｍで攪拌しながら、該反応容器に５３０ｍＬ／分で添加し、ｐＨコントローラーにより反応容器に供給されるアンモニア水と反応させた。このとき、反応温度（反応容器の内温）は２０℃〜３０℃の範囲であった。混合溶液の添加終了後、引き続き、反応容器内を攪拌しながら１時間保持し、次いで、２５質量％アンモニア水を供給して、スラリー状の生成物を得た。得られたスラリー状の生成物を濾過し、リンス洗浄した後、固形物（ケーキ）を得た。なお、反応容器に供給されたアンモニア水の合計量は９０ｋｇであり、オキシ硫酸チタンを水酸化チタンに変えるために必要な理論量の２倍であった。
(Production Example 1-Preparation of titanium oxide particle dispersion)
A reaction vessel comprising a pH electrode and a pH controller connected to the pH electrode and having a mechanism for adjusting the pH to a constant level by supplying 25% by mass of aqueous ammonia (that is, in this reaction vessel, When the pH became lower than the set value, ammonia water began to be supplied and continuously supplied until the pH reached the set value), and 30 kg of ion-exchanged water was added, and the set value of the pH controller was set to pH 4. On the other hand, after dissolving 75 kg of titanium oxysulfate in 50 kg of ion-exchanged water, 30 kg of 35% hydrogen peroxide solution was added to the obtained aqueous solution under cooling to prepare a mixed solution. The mixed solution was added to the reaction vessel at 530 mL / min while stirring the reaction vessel at 42 rpm, and reacted with ammonia water supplied to the reaction vessel by a pH controller. At this time, the reaction temperature (internal temperature of the reaction vessel) was in the range of 20 ° C to 30 ° C. After the addition of the mixed solution was completed, the inside of the reaction vessel was kept for 1 hour with stirring, and then 25% by mass ammonia water was supplied to obtain a slurry product. The obtained slurry-like product was filtered and rinsed, and then a solid (cake) was obtained. The total amount of ammonia water supplied to the reaction vessel was 90 kg, which was twice the theoretical amount required to change titanium oxysulfate to titanium hydroxide.
上記で得られた固形物（ケーキ）をステンレス製バット（３０ｃｍ×４０ｃｍ）１２枚に２．３ｋｇずつ分け入れ、このバット１２枚を箱型乾燥機（旭科学製「スーパーテンプオーブン ＨＰ−６０」、内容積：２１６リットル）に入れて、４０ｍ3／ｈｒの乾燥空気流通下、１１５℃で５時間保持した後、引き続き２５０℃で５時間保持することにより乾燥を行ない、ＢＥＴ表面積が１８．０ｍ2／ｇの乾燥粉末を得た。このときの乾燥機内の最大水蒸気分圧は２７．４ｋＰａであった。得られた乾燥粉末を３５０℃の空気雰囲気下で２時間焼成し、その後、室温まで冷却して、粒子状光触媒体である酸化チタン粉末を合計２２ｋｇ得た。 The solid matter (cake) obtained above was divided into 2.3 kg each in 12 stainless steel bats (30 cm × 40 cm), and the 12 bats were put into a box-type dryer (“Supertempo oven HP-60” manufactured by Asahi Kagaku). , Inner volume: 216 liters) and kept at 115 ° C. for 5 hours under a flow of dry air of 40 m 3 / hr, followed by drying at 250 ° C. for 5 hours to achieve a BET surface area of 18.0 m 2. / G dry powder was obtained. The maximum water vapor partial pressure in the dryer at this time was 27.4 kPa. The obtained dry powder was calcined in an air atmosphere at 350 ° C. for 2 hours, and then cooled to room temperature to obtain a total of 22 kg of titanium oxide powder as a particulate photocatalyst.
次に、イオン交換水８７．６ｋｇにリン酸二水素アンモニウム９５０ｇ（和光特級試薬）を溶解させ、さらに上記で得られた酸化チタン粉末２２ｋｇを加えて混合物を得た。この混合物を、媒体攪拌式分散機（シンマルエンタープライゼス製「ダイノーミルＫＤＬ−ＰＩＬＯＴ Ａ型」）を用いて下記の条件で分散処理して、酸化チタン粒子分散液を得た。
分散媒体：直径０．３ｍｍのジルコニア製ビーズ ４．２ｋｇ
処理温度：２０℃
合計処理時間：約２４０分間
攪拌速度：周速８ｍ／秒
流速：２Ｌ／分
処理液循環：あり
Next, 950 g of ammonium dihydrogen phosphate (Wako Special Grade Reagent) was dissolved in 87.6 kg of ion-exchanged water, and 22 kg of the titanium oxide powder obtained above was further added to obtain a mixture. This mixture was subjected to dispersion treatment under the following conditions using a medium stirring type disperser (“Dynomill KDL-PILOT A type” manufactured by Shinmaru Enterprises Co., Ltd.) to obtain a titanium oxide particle dispersion.
Dispersion medium: Zirconia beads with a diameter of 0.3 mm 4.2 kg
Processing temperature: 20 ° C
Total treatment time: about 240 minutes Stirring speed: peripheral speed 8m / sec Flow rate: 2L / min Treatment liquid circulation: yes
さらに、上記で得られた酸化チタン粒子分散液に、媒体攪拌式分散機（コトブキ技研社製「ウルトラアペックスミルＵＡＭ−５」）を用いて下記条件で２回目の分散処理を施した。
分散媒体：直径０．０５ｍｍのジルコニア製ビーズ１３ｋｇ
処理温度：２０℃
合計処理時間：約４００分間
回転数：２０００ｒｐｍ
流速：１Ｌ／分
処理液循環：あり
Furthermore, the titanium oxide particle dispersion obtained above was subjected to a second dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM-5” manufactured by Kotobuki Giken Co., Ltd.).
Dispersion medium: 13 kg of zirconia beads having a diameter of 0.05 mm
Processing temperature: 20 ° C
Total processing time: about 400 minutes Rotation speed: 2000 rpm
Flow rate: 1L / min Treatment liquid circulation: Yes
得られた酸化チタン粒子分散液中のリン酸アンモニウム塩の含有量は、酸化チタン粒子に対して０．０３モル倍である。また、上記で得られた分散液を遠心分離して粗粒分を除去したところ、平均分散粒子径は８４ｎｍであった。また、得られた分散液の固形分濃度が１０質量％になるように水で調整したところ、この分散液のｐＨは６．９であった。なお、分散処理前の混合物中の固形分と、分散処理（上記２回目の分散処理）後の分散液中の固形分とについて、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、どちらも結晶型はアナターゼ型であり、分散処理による結晶型の変化は見られなかった。 The content of ammonium phosphate in the obtained titanium oxide particle dispersion is 0.03 mol times with respect to the titanium oxide particles. Moreover, when the dispersion liquid obtained above was centrifuged to remove coarse particles, the average dispersed particle diameter was 84 nm. Moreover, when it adjusted with water so that solid content concentration of the obtained dispersion liquid might be 10 mass%, pH of this dispersion liquid was 6.9. The solid content in the mixture before the dispersion treatment and the solid content in the dispersion after the dispersion treatment (the second dispersion treatment above) were measured and compared with each other. The type was anatase type, and no change in crystal type due to dispersion treatment was observed.
（製造例２−酸化タングステン粒子分散液の調製）
パラタングステン酸アンモニウム（日本無機化学製）を空気中７００℃で６時間焼成して、粒子状光触媒体である酸化タングステン粉末を得た。
次に、イオン交換水４ｋｇに、上記で得られた酸化タングステン粉末１ｋｇを加えて混合物を得た。この混合物を、媒体攪拌式分散機（コトブキ技研社製「ウルトラアペックスミル ＵＡＭ−１ １００９」）を用いて下記の条件で分散処理して、酸化タングステン粒子分散液を得た。
分散媒体：直径０．０５ｍｍのジルコニア製ビーズ１．８５ｋｇ
攪拌速度：周速１２．６ｍ／秒
流速：０．２５Ｌ／分
合計処理時間：約５０分
(Production Example 2-Preparation of tungsten oxide particle dispersion)
Ammonium paratungstate (manufactured by Nippon Inorganic Chemical Co., Ltd.) was calcined in air at 700 ° C. for 6 hours to obtain a tungsten oxide powder as a particulate photocatalyst.
Next, 1 kg of the tungsten oxide powder obtained above was added to 4 kg of ion-exchanged water to obtain a mixture. This mixture was subjected to a dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM-1 1009” manufactured by Kotobuki Giken Co., Ltd.) to obtain a tungsten oxide particle dispersion.
Dispersion medium: 1.85 kg of zirconia beads having a diameter of 0.05 mm
Stirring speed: peripheral speed 12.6 m / sec Flow rate: 0.25 L / min Total processing time: about 50 minutes
得られた酸化タングステン粒子分散液における酸化タングステン粒子の平均分散粒子径は１１４ｎｍであった。また、得られた分散液の固形分濃度が１０質量％になるように水で調整したところ、この分散液のｐＨは３．０であった。また、この分散液の一部を真空乾燥することにより得られた固形分のＢＥＴ比表面積は３４ｍ2／ｇであった。なお、分散処理前の混合物中の固形分と、分散処理後の分散液中の固形分とについて、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、どちらも結晶型はＷＯ3であり、分散処理による結晶型の変化は見られなかった。 The average dispersed particle diameter of the tungsten oxide particles in the obtained tungsten oxide particle dispersion was 114 nm. Moreover, when it adjusted with water so that solid content concentration of the obtained dispersion liquid might be 10 mass%, pH of this dispersion liquid was 3.0. Moreover, the BET specific surface area of solid content obtained by vacuum-drying a part of this dispersion liquid was 34 m < 2 > / g. In addition, when the solid content in the mixture before the dispersion treatment and the solid content in the dispersion liquid after the dispersion treatment were measured and compared with each other, the crystal form was WO 3 and both were dispersed. There was no change in crystal form due to treatment.
（実施例１）
製造例１で得た酸化チタン粒子分散液と、製造例２で得た酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．８であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．０９５ｈ-1であった。
Example 1
Mix the titanium oxide particle dispersion obtained in Production Example 1 and the tungsten oxide particle dispersion obtained in Production Example 2 so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). As a result, a photocatalyst dispersion liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.8. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.095 h −1 .
（比較例１）
製造例１で得た酸化チタン粒子分散液に代えて、市販の酸化チタン粒子分散液（石原産業社製「ＳＴＳ−０１」、硝酸含有、平均分散粒子径：５０ｎｍ）を用いたこと以外は、実施例１と同様に操作して、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは１．９であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に凝集粒子が生成し、固液分離が起こった。
(Comparative Example 1)
In place of the titanium oxide particle dispersion obtained in Production Example 1, a commercially available titanium oxide particle dispersion (“STS-01” manufactured by Ishihara Sangyo Co., Ltd., nitric acid-containing, average dispersed particle diameter: 50 nm) was used. The photocatalyst dispersion liquid was obtained in the same manner as in Example 1. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 1.9. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, aggregated particles were generated during storage, and solid-liquid separation occurred.
（実施例２）
製造例１で得た酸化チタン粒子分散液と、製造例２で得た酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合した。次いで、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０３質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の５質量％となるように加えて、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 2)
Mix the titanium oxide particle dispersion obtained in Production Example 1 and the tungsten oxide particle dispersion obtained in Production Example 2 so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). did. Next, the aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) is 0.03 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms. In addition, methanol was added so that the concentration thereof was 5% by mass of the total solvent to obtain a photocatalyst dispersion. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration of 5% by mass).
At this point, when the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
さらに、上記光触媒体分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、超高圧水銀灯（ウシオ電機製、ランプハウス：「ＭＰＬ−２５１０１」、超高圧水銀灯：「ＵＳＨ−２５０ＢＹ」、ランプ電源：「ＨＢ−２５１０３ＢＹ」）にて光照射（紫外線照射）を２時間行うことにより、光触媒体分散液中のヘキサクロロ白金酸を白金に還元して、光触媒体分散液を得た。この光照射後の光触媒体分散液のｐＨは４．６であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１２９ｈ-1であった。
Further, 30 g of the above photocatalyst dispersion liquid was transferred to a 100 mL beaker, and while stirring, an ultrahigh pressure mercury lamp (manufactured by USHIO INC., Lamp house: “MPL-25101”, ultrahigh pressure mercury lamp: “USH-250BY”, lamp power supply: “HB −25103BY ”) was subjected to light irradiation (ultraviolet irradiation) for 2 hours to reduce hexachloroplatinic acid in the photocatalyst dispersion liquid to platinum, thereby obtaining a photocatalyst dispersion liquid. The pH of the photocatalyst dispersion after the light irradiation was 4.6.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.129 h −1 .
（実施例３）
ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液の使用量を、ヘキサクロロ白金酸が白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０６質量部となるようにしたこと以外は、実施例２と同様に操作して、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 3)
The amount of hexachloroplatinic acid (H 2 PtCl 6 ) aqueous solution used is 0.06 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms. A photocatalyst dispersion liquid was obtained in the same manner as in Example 2 except that. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration of 5% by mass).
At this point, when the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
さらに、上記光触媒体分散液３０ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、光触媒体分散液中のヘキサクロロ白金酸を白金に還元して、光触媒体分散液を得た。この光照射後の光触媒体分散液のｐＨは４．５であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１３２ｈ-1であった。
Further, 30 g of the above photocatalyst dispersion liquid was transferred to a 100 mL beaker, and light irradiation was carried out in the same manner as in Example 2 to reduce hexachloroplatinic acid in the photocatalyst dispersion liquid to platinum, thereby producing a photocatalyst dispersion liquid. Got. The pH of the photocatalyst dispersion liquid after the light irradiation was 4.5.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.132 h −1 .
（実施例４）
ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液の使用量を、ヘキサクロロ白金酸が白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．１質量部となるようにしたこと以外は、実施例２と同様に操作して、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Example 4
The amount of hexachloroplatinic acid (H 2 PtCl 6 ) aqueous solution used is 0.1 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms. A photocatalyst dispersion liquid was obtained in the same manner as in Example 2 except that. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration of 5% by mass).
At this point, when the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
さらに、上記光触媒体分散液３０ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、光触媒体分散液中のヘキサクロロ白金酸を白金に還元して、光触媒体分散液を得た。この光照射後の光触媒体分散液のｐＨは４．３であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１２８ｈ-1であった。
Further, 30 g of the above photocatalyst dispersion liquid was transferred to a 100 mL beaker, and light irradiation was carried out in the same manner as in Example 2 to reduce hexachloroplatinic acid in the photocatalyst dispersion liquid to platinum, thereby producing a photocatalyst dispersion liquid. Got. The pH of the photocatalyst dispersion liquid after the light irradiation was 4.3.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.128 h −1 .
（実施例５）
ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液に代えて、テトラクロロ金酸（ＨＡｕＣｌ４）の水溶液を、テトラクロロ金酸が金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０３質量部となるように加えたこと以外は、実施例２と同様に操作して、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 5)
Instead of an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ), an aqueous solution of tetrachloroauric acid (HAuCl 4 ) was used, and the total amount of tetrachloroauric acid used as titanium atoms and tungsten oxide particles in terms of gold atoms was 100 parts by mass. A photocatalyst dispersion liquid was obtained in the same manner as in Example 2 except that 0.03 part by mass was added. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration of 5% by mass).
At this point, when the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
さらに、上記光触媒体分散液３０ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、光触媒体分散液中のテトラクロロ金酸を金に還元して、光触媒体分散液を得た。この光照射後の光触媒体分散液のｐＨは４．１であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１０９ｈ-1であった。
Further, 30 g of the above photocatalyst dispersion liquid was transferred to a 100 mL beaker and subjected to light irradiation in the same manner as in Example 2 to reduce the tetrachloroauric acid in the photocatalyst dispersion liquid to gold, thereby dispersing the photocatalyst dispersion. A liquid was obtained. The pH of the photocatalyst dispersion after the light irradiation was 4.1.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.109 h −1 .
（実施例６）
製造例２で得た酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０３質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の６．５質量％となるように加えて、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は３．３質量部（固形分濃度３．３質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 6)
An aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) is added to the tungsten oxide particle dispersion obtained in Production Example 2, and the hexachloroplatinic acid is converted to platinum atoms in an amount of 0.03 mass per 100 mass parts of the tungsten oxide particles used. In addition, methanol was added so that the concentration thereof was 6.5% by mass of the total solvent, to obtain a hexachloroplatinic acid-containing tungsten oxide particle dispersion. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 3.3 parts by mass (solid content concentration: 3.3% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the hexachloroplatinic acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce the hexachloroplatinic acid in the dispersion to platinum. A platinum-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記白金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金の含有量は、白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０１５質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．６であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１３１ｈ-1であった。
Next, the platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the platinum content in the dispersion was 0.015 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms). A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.6. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.131 h −1 .
（実施例７）
ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液の使用量を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０６質量部となるようにしたこと以外は、実施例６と同様に操作して、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 7)
Implementation was carried out except that the amount of hexachloroplatinic acid (H 2 PtCl 6 ) used was 0.06 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms. In the same manner as in Example 6, a hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 5 parts by mass (solid content concentration 5% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the hexachloroplatinic acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce the hexachloroplatinic acid in the dispersion to platinum. A platinum-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記白金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金の含有量は、白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０３質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．６であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１２５ｈ-1であった。
Next, the platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the platinum content in the dispersion was 0.03 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms), and photocatalyst dispersion A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.6. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.125 h −1 .
（実施例８）
ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液の使用量を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．１２質量部となるようにしたこと以外は、実施例６と同様に操作して、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 8)
Except that the amount of hexachloroplatinic acid (H 2 PtCl 6 ) aqueous solution used was 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms in terms of hexachloroplatinic acid. In the same manner as in Example 6, a hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 5 parts by mass (solid content concentration 5% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the hexachloroplatinic acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce the hexachloroplatinic acid in the dispersion to platinum. A platinum-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記白金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金の含有量は、白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．５であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１１４ｈ-1であった。
Next, the platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (As a result, the platinum content in the dispersion was 0.06 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms), and photocatalyst dispersion A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.5. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the obtained photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.114 h −1 .
（実施例９）
ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液の使用量を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．２質量部となるようにしたこと以外は、実施例６と同様に操作して、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Example 9
Except that the amount of hexachloroplatinic acid (H 2 PtCl 6 ) used was 0.2 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of platinum atoms. In the same manner as in Example 6, a hexachloroplatinic acid-containing tungsten oxide particle dispersion was obtained. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 5 parts by mass (solid content concentration 5% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the hexachloroplatinic acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce the hexachloroplatinic acid in the dispersion to platinum. A platinum-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記白金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金の含有量は、白金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．１質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．３であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１２０ｈ-1であった。
Next, the platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the platinum content in the dispersion was 0.1 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum atoms). A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.3. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.120 h −1 .
（実施例１０）
製造例２で得た酸化タングステン粒子分散液に、テトラクロロ金酸（ＨＡｕＣｌ4）の水溶液を、テトラクロロ金酸が金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０３質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の６．５質量％となるように加えて、テトラクロロ金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は３．３質量部（固形分濃度３．３質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 10)
To the tungsten oxide particle dispersion obtained in Production Example 2, an aqueous solution of tetrachloroauric acid (HAuCl 4 ) is added in an amount of 0.03 mass per 100 parts by mass of tungsten oxide particles in terms of gold atoms in terms of tetrachloroauric acid. Further, methanol was added so that the concentration thereof was 6.5% by mass of the total solvent to obtain a tetrachloroauric acid-containing tungsten oxide particle dispersion. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 3.3 parts by mass (solid content concentration: 3.3% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記テトラクロロ金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のテトラクロロ金酸を金に還元して、金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the tetrachloroauric acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce tetrachloroauric acid in the dispersion to gold. Thus, a gold-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の金の含有量は、金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０１５質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．５であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１０６ｈ-1であった。
Next, the gold-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the gold content in the dispersion was 0.015 parts by mass in terms of gold atoms with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles). A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.5. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.106 h −1 .
（実施例１１）
テトラクロロ金酸（ＨＡｕＣｌ4）水溶液の使用量を、テトラクロロ金酸が金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．１２質量部となるようにしたこと以外は、実施例１０と同様に操作して、テトラクロロ金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
(Example 11)
Implementation was carried out except that the amount of tetrachloroauric acid (HAuCl 4 ) aqueous solution used was 0.12 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of gold atoms. In the same manner as in Example 10, a tetrachloroauric acid-containing tungsten oxide particle dispersion was obtained. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 5 parts by mass (solid content concentration 5% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記テトラクロロ金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のテトラクロロ金酸を金に還元して、金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the tetrachloroauric acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce tetrachloroauric acid in the dispersion to gold. Thus, a gold-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の金の含有量は、金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．５であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１４１ｈ-1であった。
Next, the gold-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the gold content in the dispersion was 0.06 parts by mass in terms of gold atoms with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles). A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.5. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 0.141 h −1 .
（実施例１２）
テトラクロロ金酸（ＨＡｕＣｌ4）水溶液の使用量を、テトラクロロ金酸が金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．２質量部となるようにしたこと以外は、実施例１０と同様に操作して、テトラクロロ金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は５質量部（固形分濃度５質量％）であった。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Example 12
Implementation was carried out except that the amount of tetrachloroauric acid (HAuCl 4 ) aqueous solution used was 0.2 parts by mass with respect to 100 parts by mass of tungsten oxide particles in terms of gold atoms. In the same manner as in Example 10, a tetrachloroauric acid-containing tungsten oxide particle dispersion was obtained. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 5 parts by mass (solid content concentration 5% by mass).
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記テトラクロロ金酸含有酸化タングステン粒子分散液２２．５ｇを１００ｍＬビーカーに移し、実施例２と同様に操作して光照射を行うことにより、分散液中のテトラクロロ金酸を金に還元して、金含有酸化タングステン粒子分散液を得た。
この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。
Next, 22.5 g of the tetrachloroauric acid-containing tungsten oxide particle dispersion is transferred to a 100 mL beaker, and light irradiation is performed in the same manner as in Example 2 to reduce tetrachloroauric acid in the dispersion to gold. Thus, a gold-containing tungsten oxide particle dispersion was obtained.
At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記金含有酸化タングステン粒子分散液と、製造例１で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の金の含有量は、金原子換算で酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．１質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは４．４であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１４６ｈ-1であった。
Next, the gold-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 1 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the gold content in the dispersion was 0.1 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of gold atoms). A liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 4.4. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.146 h −1 .
（製造例３−酸化チタン粒子分散液の調製）
リン酸二水素アンモニウム（和光特級試薬）０．０８６ｇを水 ４７．１ｇに溶解させ、得られたリン酸二水素アンモニウム水溶液に、硫酸チタニルの加熱加水分解により得られたメタチタン酸の固形物（ケーキ）（ＴｉＯ２として固形分濃度４６．８質量％）１２．８２ｇを混合した。このとき、リン酸二水素アンモニウムの量は、メタチタン酸１モルに対して０．０１ モルであった。得られた混合物を、媒体攪拌式粉砕機（五十嵐機械製作所製「４ＴＳＧ−１／８」）を用いて下記の条件で分散処理して、酸化チタン粒子分散液を得た。
媒体：直径０．０５ｍｍのジルコニア製ビーズ １９０ｇ
処理温度：２０℃
処理時間：１時間
回転数：２０００ｒｐｍ
(Production Example 3-Preparation of titanium oxide particle dispersion)
0.086 g of ammonium dihydrogen phosphate (Wako Special Grade Reagent) was dissolved in 47.1 g of water, and the resulting ammonium dihydrogen phosphate aqueous solution was obtained by subjecting titanyl sulfate to thermal hydrolysis to a solid product (cake) of metatitanic acid. ) (Solid content concentration 46.8% by mass as TiO 2 ) 12.82 g was mixed. At this time, the amount of ammonium dihydrogen phosphate was 0.01 mol with respect to 1 mol of metatitanic acid. The obtained mixture was subjected to a dispersion treatment under the following conditions using a medium stirring pulverizer (“4TSG-1 / 8” manufactured by Igarashi Machinery Co., Ltd.) to obtain a titanium oxide particle dispersion.
Medium: 190 g zirconia beads with a diameter of 0.05 mm
Processing temperature: 20 ° C
Processing time: 1 hour Rotation speed: 2000 rpm
得られた酸化チタン粒子分散液中の酸化チタン粒子の平均分散粒子径は９２ｎｍであり、分散液のｐＨは７．８ であった。なお、分散処理前の混合物と分散処理後の分散液との一部を真空乾燥して固形分を得、各固形分のＸ線回折スペクトルをそれぞれ測定して比較したところ、どちらも結晶型はアナターゼ型であり、分散処理による結晶型の変化は見られなかった。 The average dispersed particle diameter of the titanium oxide particles in the obtained titanium oxide particle dispersion was 92 nm, and the pH of the dispersion was 7.8. A part of the mixture before the dispersion treatment and the dispersion after the dispersion treatment were vacuum-dried to obtain a solid content, and the X-ray diffraction spectrum of each solid content was measured and compared. It was anatase type, and no change in crystal form due to dispersion treatment was observed.
（製造例４−酸化タングステン粒子分散液の調製）
イオン交換水４ｋｇに、粒子状の光触媒体である酸化タングステン粉末（日本無機化学製）１ｋｇを加えて混合して混合物を得た。この混合物を、媒体攪拌式分散機（コトブキ技研社製「ウルトラアペックスミル ＵＡＭ−１ １００９」）を用いて下記の条件で分散処理して、酸化タングステン粒子分散液を得た。
分散媒体：直径０．０５ｍｍのジルコニア製ビーズ１．８５ｋｇ
攪拌速度：周速１２．６ｍ／秒
流速：０．２５Ｌ／分
合計処理時間：約５０分
(Production Example 4-Preparation of tungsten oxide particle dispersion)
1 kg of tungsten oxide powder (manufactured by Nippon Inorganic Chemical Co., Ltd.), which is a particulate photocatalyst, was added to 4 kg of ion exchange water and mixed to obtain a mixture. This mixture was subjected to a dispersion treatment under the following conditions using a medium stirring type disperser (“Ultra Apex Mill UAM-1 1009” manufactured by Kotobuki Giken Co., Ltd.) to obtain a tungsten oxide particle dispersion.
Dispersion medium: 1.85 kg of zirconia beads having a diameter of 0.05 mm
Stirring speed: peripheral speed 12.6 m / sec Flow rate: 0.25 L / min Total processing time: about 50 minutes
得られた酸化タングステン粒子分散液における酸化タングステン粒子の平均分散粒子径は１１８ｎｍであった。また、この分散液の一部を真空乾燥して固形分を得たところ、得られた固形分のＢＥＴ比表面積は４０ｍ2／ｇであった。なお、分散処理の前の混合物についても同様に真空乾燥して固形分を得、分散処理前の混合物の固形分と分散処理後の分散液の固形分について、Ｘ線回折スペクトルをそれぞれ測定して比較したところ、どちらも結晶型はＷＯ3であり、分散処理による結晶型の変化は見られなかった。この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。 The average dispersed particle diameter of the tungsten oxide particles in the obtained tungsten oxide particle dispersion was 118 nm. Moreover, when a part of this dispersion was vacuum-dried to obtain a solid content, the BET specific surface area of the obtained solid content was 40 m 2 / g. Similarly, the mixture before the dispersion treatment is also vacuum-dried to obtain a solid content, and X-ray diffraction spectra are respectively measured for the solid content of the mixture before the dispersion treatment and the solid content of the dispersion after the dispersion treatment. As a result of comparison, the crystal form of both was WO 3 , and no change in crystal form due to dispersion treatment was observed. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
（実施例１３）
製造例４で得た酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．１２質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の６．２５質量％となるように加えて、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は１１．４質量部（固形分濃度１１．４質量％）であった。
(Example 13)
An aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) is added to the tungsten oxide particle dispersion obtained in Production Example 4, and the hexachloroplatinic acid is converted to platinum atoms in an amount of 0.12 mass per 100 mass parts of the tungsten oxide particles used. In addition, methanol was added so that the concentration thereof was 6.25% by mass of the total solvent, to obtain a hexachloroplatinic acid-containing tungsten oxide particle dispersion. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 11.4 parts by mass (solid content concentration 11.4% by mass).
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液４８０ｇを１Ｌビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３時間行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。この光照射後の光触媒体分散液のｐＨは２．４であった。 この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。 Next, 480 g of the hexachloroplatinic acid-containing tungsten oxide particle dispersion is transferred to a 1 L beaker and stirred, while stirring, a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B- B ") was subjected to light irradiation (ultraviolet irradiation) for 3 hours to reduce the hexachloroplatinic acid in the dispersion to platinum to obtain a platinum-containing tungsten oxide particle dispersion. The pH of the photocatalyst dispersion after the light irradiation was 2.4. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage.
次いで、上記白金含有酸化タングステン粒子分散液と、製造例３で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金の含有量は、白金原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して０．０６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）は５質量部（固形分濃度５質量％）であり、ｐＨは３．６であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（アセトアルデヒドの分解）を評価したところ、一次反応速度定数は０．１８２ｈ-1であった。
Next, the platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 3 are mixed so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Thus, the platinum content in the dispersion was 0.06 parts by mass in terms of platinum atoms with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles), and the photocatalyst. A dispersion was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 5 parts by mass (solid content concentration 5% by mass), and the pH was 3.6. .
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of acetaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.182 h −1 .
（実施例１４）
製造例４で得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．６４４ｈ-1であった。
(Example 14)
When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid obtained in Production Example 4 was evaluated, the first-order rate constant was 0.644 h −1 .
（実施例１５）
製造例４で得た酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０９６質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）を、水により１０．２質量部（固形分濃度１０．２質量％）に調整した。
(Example 15)
In the tungsten oxide particle dispersion obtained in Production Example 4, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) hexachloroplatinic acid (H 2 PtCl 6 ) is used, and the amount of tungsten oxide particles used in terms of platinum atoms is 100 Add to 0.096 parts by mass with respect to parts by mass, and further add methanol so that the concentration is 1.1% by mass of the total solvent to obtain a hexachloroplatinic acid-containing tungsten oxide particle dispersion. It was. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was adjusted to 10.2 parts by mass (solid content concentration 10.2% by mass) with water.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。 Next, 30 g of the above hexachloroplatinic acid-containing tungsten oxide particle dispersion was transferred to a 100 mL beaker and stirred, while stirring, a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B- B ") was irradiated with light (ultraviolet irradiation) for 30 minutes to reduce the hexachloroplatinic acid in the dispersion to platinum to obtain a platinum-containing tungsten oxide particle dispersion.
次いで、上記白金含有酸化タングステン粒子分散液に、塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液（ＰｄＣｌ2粉末０．２５２ｇを、濃度１ｍｏｌ／Ｌの塩酸水溶液９．４１ｇと水９０．４３ｇからなる水溶液に溶解）を、塩化パラジウムがパラジウム原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０２４質量部となるように加え、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中の塩化パラジウムをパラジウムに還元して、パラジウム及び白金含有酸化タングステン粒子分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化タングステン粒子との合計量）は１０．０質量部（固形分濃度１０．０質量％）であった。この光照射後の光触媒体分散液のｐＨは２．２であった。 Next, a palladium chloride (PdCl 2 ) hydrochloric acid aqueous solution (PdCl 2 powder 0.252 g) was dissolved in the platinum-containing tungsten oxide particle dispersion in an aqueous solution composed of 9.41 g of hydrochloric acid aqueous solution having a concentration of 1 mol / L and 90.43 g of water. ) Is added so that the palladium chloride is 0.024 parts by mass with respect to 100 parts by mass of the tungsten oxide particles in terms of palladium atoms, and is stirred, and a high pressure mercury lamp (manufactured by Ushio Electric, high pressure mercury lamp: “UM- 102 ”, high-pressure mercury lamp lighting device:“ UM-103B-B ”), by performing light irradiation (ultraviolet irradiation) for 30 minutes, palladium chloride in the dispersion is reduced to palladium, and palladium and platinum-containing oxidation A tungsten particle dispersion was obtained. The solid content (total amount with the tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 10.0 parts by mass (solid content concentration 10.0% by mass). The pH of the photocatalyst dispersion after the light irradiation was 2.2.
次いで、上記パラジウム及び白金含有酸化タングステン粒子分散液と、製造例３で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金及びパラジウムの含有量は、白金及びパラジウム原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対してそれぞれ０．０４８質量部と０．０１２質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に調整した。ｐＨは３．９であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は１．０５ｈ-1であった。
Next, the palladium- and platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 3 are set so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (By this, the content of platinum and palladium in the dispersion is 0.048 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum and palladium atoms, respectively) And 0.012 parts by mass) to obtain a photocatalyst dispersion. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass). The pH was 3.9.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 1.05 h −1 .
（実施例１６）
製造例４で得た酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０９６質量部となるように加え、引き続き、実施例１５の塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液を、塩化パラジウムがパラジウム原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０２４質量部となるように加えた。その後、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、ヘキサクロロ白金酸及び塩化パラジウム含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）を、水により１０．０質量部（固形分濃度１０．０質量％）に調整した。
(Example 16)
In the tungsten oxide particle dispersion obtained in Production Example 4, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) hexachloroplatinic acid (H 2 PtCl 6 ) is used, and the amount of tungsten oxide particles used in terms of platinum atoms is 100 Subsequently, the aqueous hydrochloric acid solution of palladium chloride (PdCl 2 ) of Example 15 was added to 100 parts by mass of tungsten oxide particles in terms of palladium atoms. It added so that it might become 0.024 mass part with respect to it. Thereafter, methanol was further added so that the concentration thereof was 1.1% by mass of the total solvent to obtain a tungsten oxide particle dispersion containing hexachloroplatinic acid and palladium chloride. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was adjusted to 10.0 parts by mass (solid content concentration 10.0% by mass) with water.
次いで、上記ヘキサクロロ白金酸及び塩化パラジウム含有酸化タングステン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を１時間行うことにより、分散液中のヘキサクロロ白金酸を白金に還元し、塩化パラジウムがパラジウムに還元して、白金及びパラジウム含有酸化タングステン粒子分散液を得た。この光照射後の光触媒体分散液のｐＨは２．３であった。 Next, 30 g of the above-mentioned hexachloroplatinic acid and palladium chloride-containing tungsten oxide particle dispersion was transferred to a 100 mL beaker, and while stirring, a high-pressure mercury lamp (manufactured by USHIO INC., High-pressure mercury lamp: “UM-102”, high-pressure mercury lamp lighting device: “UM” -103B-B ") is subjected to light irradiation (ultraviolet irradiation) for 1 hour, whereby hexachloroplatinic acid in the dispersion is reduced to platinum, palladium chloride is reduced to palladium, and platinum and palladium-containing tungsten oxide particles. A dispersion was obtained. The pH of the photocatalyst dispersion after the light irradiation was 2.3.
次いで、上記白金及びパラジウム含有酸化タングステン粒子分散液と、製造例３で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金及びパラジウムの含有量は、白金及びパラジウム原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対してそれぞれ０．０４８質量部と０．０１２質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に調整した。ｐＨは３．９であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．９５９ｈ-1であった。
Next, the platinum and palladium-containing tungsten oxide particle dispersion liquid and the titanium oxide particle dispersion liquid obtained in Production Example 3 are set so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (By this, the content of platinum and palladium in the dispersion is 0.048 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum and palladium atoms, respectively) And 0.012 parts by mass) to obtain a photocatalyst dispersion. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass). The pH was 3.9.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.959 h −1 .
（実施例１７）
製造例４で得た酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０４８質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）を、水により１０．５質量部（固形分濃度１０．５質量％）に調整した。
(Example 17)
In the tungsten oxide particle dispersion obtained in Production Example 4, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) hexachloroplatinic acid (H 2 PtCl 6 ) is used, and the amount of tungsten oxide particles used in terms of platinum atoms is 100 In addition to adding 0.048 parts by mass with respect to parts by mass, methanol is further added so that the concentration thereof becomes 1.1% by mass of the total solvent to obtain a hexachloroplatinic acid-containing tungsten oxide particle dispersion. It was. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was adjusted to 10.5 parts by mass (solid content concentration 10.5% by mass) with water.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。 Next, 30 g of the above hexachloroplatinic acid-containing tungsten oxide particle dispersion was transferred to a 100 mL beaker and stirred, while stirring, a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B- B ") was irradiated with light (ultraviolet irradiation) for 30 minutes to reduce the hexachloroplatinic acid in the dispersion to platinum to obtain a platinum-containing tungsten oxide particle dispersion.
次いで、上記白金含有酸化タングステン粒子分散液に、実施例１５で用いた塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液を、塩化パラジウムがパラジウム原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０７２質量部となるように加え、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中の塩化パラジウムをパラジウムに還元して、パラジウム及び白金含有酸化タングステン粒子分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化タングステン粒子との合計量）は１０．０質量部（固形分濃度１０．０質量％）であった。この光照射後の光触媒体分散液のｐＨは２．０であった。 Next, the hydrochloric acid aqueous solution of palladium chloride (PdCl 2 ) used in Example 15 was added to the platinum-containing tungsten oxide particle dispersion solution in an amount of 0.000 parts by mass with respect to 100 parts by mass of the tungsten oxide particles in terms of palladium atoms. In addition to being 072 parts by mass, while stirring, light irradiation (ultraviolet irradiation) with a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B-B”) ) For 30 minutes to reduce palladium chloride in the dispersion to palladium to obtain a palladium and platinum-containing tungsten oxide particle dispersion. The solid content (total amount with the tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was 10.0 parts by mass (solid content concentration 10.0% by mass). The pH of the photocatalyst dispersion liquid after the light irradiation was 2.0.
次いで、上記パラジウム及び白金含有酸化タングステン粒子分散液と、製造例３で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金及びパラジウムの含有量は、白金及びパラジウム原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対してそれぞれ０．０２４質量部と０．０３６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に調整した。ｐＨは３．８であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．９７６ｈ-1であった。
Next, the palladium- and platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 3 are set so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (By this, the platinum and palladium contents in the dispersion liquid are each 0.024 parts by mass in terms of platinum and palladium atoms with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles used. And a photocatalyst dispersion liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass). The pH was 3.8.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.976 h −1 .
（実施例１8）
製造例４で得た酸化タングステン粒子分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）の水溶液を、ヘキサクロロ白金酸が白金原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０２４質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、ヘキサクロロ白金酸含有酸化タングステン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）を、水により１０．７質量部（固形分濃度１０．７質量％）に調整した。
(Example 18)
In the tungsten oxide particle dispersion obtained in Production Example 4, an aqueous solution of hexachloroplatinic acid (H 2 PtCl 6 ) hexachloroplatinic acid (H 2 PtCl 6 ) is used, and the amount of tungsten oxide particles used in terms of platinum atoms is 100 In addition to 0.024 parts by mass with respect to parts by mass, methanol is further added so that the concentration thereof becomes 1.1% by mass of the total solvent to obtain a hexachloroplatinic acid-containing tungsten oxide particle dispersion. It was. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was adjusted to 10.7 parts by mass (solid content concentration 10.7% by mass) with water.
次いで、上記ヘキサクロロ白金酸含有酸化タングステン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中のヘキサクロロ白金酸を白金に還元して、白金含有酸化タングステン粒子分散液を得た。 Next, 30 g of the above hexachloroplatinic acid-containing tungsten oxide particle dispersion was transferred to a 100 mL beaker and stirred, while stirring, a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B- B ") was irradiated with light (ultraviolet irradiation) for 30 minutes to reduce the hexachloroplatinic acid in the dispersion to platinum to obtain a platinum-containing tungsten oxide particle dispersion.
次いで、上記白金含有酸化タングステン粒子分散液に、実施例１５で用いた塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液を、塩化パラジウムがパラジウム原子換算で酸化タングステン粒子の使用量１００質量部に対して０．０９６質量部となるように加え、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中の塩化パラジウムをパラジウムに還元して、パラジウム及び白金含有酸化タングステン粒子分散液を得た。この光照射後の光触媒体分散液のｐＨは２．０であった。この分散液１００質量部中に含まれる固形分（酸化タングステン粒子の量）は１０．０質量部（固形分濃度１０．０質量％）であった。 Next, the hydrochloric acid aqueous solution of palladium chloride (PdCl 2 ) used in Example 15 was added to the platinum-containing tungsten oxide particle dispersion solution in an amount of 0.000 parts by mass with respect to 100 parts by mass of the tungsten oxide particles in terms of palladium atoms. In addition to 096 parts by mass, with stirring, light irradiation (ultraviolet irradiation) with a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B-B”) ) For 30 minutes to reduce palladium chloride in the dispersion to palladium to obtain a palladium and platinum-containing tungsten oxide particle dispersion. The pH of the photocatalyst dispersion liquid after the light irradiation was 2.0. The solid content (amount of tungsten oxide particles) contained in 100 parts by mass of this dispersion was 10.0 parts by mass (solid content concentration 10.0% by mass).
次いで、上記パラジウム及び白金含有酸化タングステン粒子分散液と、製造例３で得た酸化チタン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の白金及びパラジウムの含有量は、白金及びパラジウム原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対してそれぞれ０．０１２質量部と０．０４８質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に調整した。ｐＨは３．７であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．９８２ｈ-1であった。
Next, the palladium- and platinum-containing tungsten oxide particle dispersion and the titanium oxide particle dispersion obtained in Production Example 3 are set so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (By this, the content of platinum and palladium in the dispersion is 0.012 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of platinum and palladium atoms, respectively) And a photocatalyst dispersion liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass). The pH was 3.7.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.982 h −1 .
（実施例１９）
製造例３で得た酸化チタン粒子分散液に、実施例１５で用いた塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液を、塩化パラジウムがパラジウム原子換算で酸化チタン粒子の使用量１００質量部に対して０．１２質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、塩化パラジウム含有酸化チタン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化チタン粒子の量）を、水により５質量部（固形分濃度５質量％）に調整した。
(Example 19)
To the titanium oxide particle dispersion obtained in Production Example 3, the hydrochloric acid aqueous solution of palladium chloride (PdCl 2 ) used in Example 15 was added to 100 parts by mass of palladium oxide in terms of palladium atoms with respect to 100 parts by mass of titanium oxide particles. In addition to adding 12 parts by mass, methanol was added so that the concentration was 1.1% by mass of the total solvent to obtain a palladium chloride-containing titanium oxide particle dispersion. The solid content (amount of titanium oxide particles) contained in 100 parts by mass of this dispersion was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water.
次いで、上記塩化パラジウム含有酸化チタン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を１時間行うことにより、分散液中の塩化パラジウムをパラジウムに還元して、パラジウム含有酸化チタン粒子分散液を得た。この光照射後の光触媒体分散液のｐＨは７．３であった。 Next, 30 g of the above palladium chloride-containing titanium oxide particle dispersion was transferred to a 100 mL beaker, and while stirring, a high-pressure mercury lamp (manufactured by USHIO, high-pressure mercury lamp: “UM-102”, high-pressure mercury lamp lighting device: “UM-103B-B” )), Light irradiation (ultraviolet irradiation) was performed for 1 hour, whereby palladium chloride in the dispersion was reduced to palladium to obtain a palladium-containing titanium oxide particle dispersion. The pH of the photocatalyst dispersion liquid after this light irradiation was 7.3.
次いで、上記パラジウム含有酸化チタン粒子分散液と、実施例１３で得た白金含有酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中のパラジウム及び白金の含有量は、パラジウム及び白金原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して共に０．０６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に水で調整した。ｐＨは３．８であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は１．０８ｈ-1であった。
Next, the palladium-containing titanium oxide particle dispersion liquid and the platinum-containing tungsten oxide particle dispersion liquid obtained in Example 13 are set so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (By this, the content of palladium and platinum in the dispersion is 0.06 parts by mass with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of palladium and platinum atoms) Thus, a photocatalyst dispersion liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water. The pH was 3.8.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 1.08 h −1 .
（実施例２０）
実施例１９で得たパラジウム含有酸化チタン粒子分散液と、実施例１３で得た白金含有酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が３：１（質量比）となるように混合して（これにより、分散液中のパラジウム及び白金の含有量は、パラジウム及び白金原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して、それぞれ０．０９質量部及び０．０３質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に水で調整した。ｐＨは４．５であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は１．７９ｈ-1であった。
(Example 20)
The palladium-containing titanium oxide particle dispersion obtained in Example 19 and the platinum-containing tungsten oxide particle dispersion obtained in Example 13 had a ratio of titanium oxide particles to tungsten oxide particles of 3: 1 (mass ratio). (Accordingly, the content of palladium and platinum in the dispersion is 0 for each 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of palladium and platinum atoms. 0.09 parts by mass and 0.03 parts by mass), to obtain a photocatalyst dispersion liquid. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water. The pH was 4.5.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 1.79 h −1 .
（実施例２１）
製造例３で得た酸化チタン粒子分散液に、実施例１５で用いた塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液を、塩化パラジウムがパラジウム原子換算で酸化チタン粒子の使用量１００質量部に対して０．０６質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、塩化パラジウム含有酸化チタン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化チタン粒子の量）を、水で５質量部（固形分濃度５質量％）に調整した。
(Example 21)
To the titanium oxide particle dispersion obtained in Production Example 3, the hydrochloric acid aqueous solution of palladium chloride (PdCl 2 ) used in Example 15 was added to 100 parts by mass of palladium oxide in terms of palladium atoms with respect to 100 parts by mass of titanium oxide particles. 0.06 parts by mass, and methanol was further added so that the concentration was 1.1% by mass of the total solvent to obtain a palladium chloride-containing titanium oxide particle dispersion. The solid content (amount of titanium oxide particles) contained in 100 parts by mass of this dispersion was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water.
次いで、上記塩化パラジウム含有酸化チタン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を１時間行うことにより、分散液中の塩化パラジウムをパラジウムに還元して、パラジウム含有酸化チタン粒子分散液を得た。この光照射後の光触媒体分散液のｐＨは７．８であった。 Next, 30 g of the above palladium chloride-containing titanium oxide particle dispersion was transferred to a 100 mL beaker, and while stirring, a high-pressure mercury lamp (manufactured by USHIO, high-pressure mercury lamp: “UM-102”, high-pressure mercury lamp lighting device: “UM-103B-B” )), Light irradiation (ultraviolet irradiation) was performed for 1 hour, whereby palladium chloride in the dispersion was reduced to palladium to obtain a palladium-containing titanium oxide particle dispersion. The pH of the photocatalyst dispersion after the light irradiation was 7.8.
次いで、上記パラジウム含有酸化チタン粒子分散液と、実施例１３で得た白金含有酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中のパラジウム及び白金の含有量は、パラジウム及び白金原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して、パラジウムが０．０３質量部、白金が０．０６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に水で調整した。ｐＨは４．０であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．９０１ｈ-1であった。
Next, the palladium-containing titanium oxide particle dispersion liquid and the platinum-containing tungsten oxide particle dispersion liquid obtained in Example 13 are set so that the ratio of titanium oxide particles to tungsten oxide particles is 1: 1 (mass ratio). (Accordingly, the content of palladium and platinum in the dispersion is 0.03 palladium relative to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of palladium and platinum atoms. Mass part, platinum became 0.06 mass part), and the photocatalyst body dispersion liquid was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water. The pH was 4.0.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.901 h −1 .
（実施例２２）
実施例１９で得たパラジウム含有酸化チタン粒子分散液と、実施例１３で得た白金含有酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が３：１（質量比）となるように混合して（これにより、分散液中のパラジウム及び白金の含有量は、パラジウム及び白金原子換算で、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して、それぞれ０．０４５質量部及び０．０３質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に水で調整した。ｐＨは４．８であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．９７８ｈ-1であった。
(Example 22)
The palladium-containing titanium oxide particle dispersion obtained in Example 19 and the platinum-containing tungsten oxide particle dispersion obtained in Example 13 had a ratio of titanium oxide particles to tungsten oxide particles of 3: 1 (mass ratio). (Accordingly, the content of palladium and platinum in the dispersion is 0 for each 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles in terms of palladium and platinum atoms. 045 parts by mass and 0.03 parts by mass), to obtain a photocatalyst dispersion. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water. The pH was 4.8.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.978 h −1 .
（実施例２３）
製造例３で得た酸化チタン粒子分散液に、テトラクロロ金酸（ＨＡｕＣｌ4）水溶液を、テトラクロロ金酸が金原子換算で酸化チタン粒子の使用量１００質量部に対して０．０６質量部となるように加え、さらに、メタノールを、その濃度が全溶媒の１．１質量％となるように加えて、テトラクロロ金酸含有酸化チタン粒子分散液を得た。この分散液１００質量部中に含まれる固形分（酸化チタン粒子の量）は５．１質量部（固形分濃度５．１質量％）であった。
次いで、上記テトラクロロ金酸含有酸化チタン粒子分散液３０ｇを１００ｍＬビーカーに移し、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中のテトラクロロ金酸を金に還元して、金含有酸化チタン粒子分散液を得た。
(Example 23)
To the titanium oxide particle dispersion obtained in Production Example 3, a tetrachloroauric acid (HAuCl 4 ) aqueous solution is added in an amount of 0.06 parts by mass with respect to 100 parts by mass of titanium oxide particles in terms of gold atoms. Further, methanol was added so that the concentration thereof was 1.1% by mass of the total solvent to obtain a tetrachloroauric acid-containing titanium oxide particle dispersion. The solid content (amount of titanium oxide particles) contained in 100 parts by mass of this dispersion was 5.1 parts by mass (solid content concentration 5.1% by mass).
Subsequently, 30 g of the above tetrachloroauric acid-containing titanium oxide particle dispersion was transferred to a 100 mL beaker and stirred, while stirring, a high pressure mercury lamp (manufactured by USHIO, high pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B” -B ") was subjected to light irradiation (ultraviolet irradiation) for 30 minutes to reduce the tetrachloroauric acid in the dispersion to gold to obtain a gold-containing titanium oxide particle dispersion.
次いで、上記金含有化チタン粒子分散液に、実施例１５で用いた塩化パラジウム（ＰｄＣｌ2）の塩酸水溶液を、塩化パラジウムがパラジウム原子換算で酸化チタン粒子の使用量１００質量部に対して０．０６質量部となるように加え、攪拌しながら、高圧水銀灯（ウシオ電機製、高圧水銀灯：「ＵＭ−１０２」、高圧水銀ランプ点灯装置：「ＵＭ−１０３Ｂ−Ｂ」）にて光照射（紫外線照射）を３０分間行うことにより、分散液中の塩化パラジウムをパラジウムに還元して、パラジウム及び金含有酸化チタン粒子分散液を得た。この光照射後の光触媒体分散液のｐＨは７．７であった。この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。この分散液１００質量部中に含まれる固形分（酸化チタン粒子の量）は５．００質量部（固形分濃度５．００質量％）であった。 Subsequently, the hydrochloric acid aqueous solution of palladium chloride (PdCl 2 ) used in Example 15 was added to the gold-containing titanium particle dispersion liquid in an amount of 0.000 parts by mass with respect to 100 parts by mass of the titanium oxide particles in terms of palladium atoms. Light irradiation (ultraviolet irradiation) with high pressure mercury lamp (manufactured by USHIO INC., High pressure mercury lamp: “UM-102”, high pressure mercury lamp lighting device: “UM-103B-B”) while stirring to be 06 parts by mass ) For 30 minutes to reduce palladium chloride in the dispersion to palladium to obtain a palladium and gold-containing titanium oxide particle dispersion. The pH of the photocatalyst dispersion liquid after the light irradiation was 7.7. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. The solid content (amount of titanium oxide particles) contained in 100 parts by mass of this dispersion was 5.00 parts by mass (solid content concentration of 5.00% by mass).
次いで、上記パラジウム及び金含有酸化チタン粒子分散液と、実施例１３で得た白金含有酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合して（これにより、分散液中の金、パラジウム及び白金の含有量は、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して、金とパラジウムが原子換算で０．０３質量部、白金が原子換算で０．０６質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に水で調整した。ｐＨは４．２であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は１．２０ｈ-1であった。
Subsequently, the palladium-and-gold-containing titanium oxide particle dispersion and the platinum-containing tungsten oxide particle dispersion obtained in Example 13 have a ratio of titanium oxide particles to tungsten oxide particles of 1: 1 (mass ratio). (Thus, the content of gold, palladium and platinum in the dispersion is 0 for gold and palladium in terms of atoms with respect to 100 parts by mass of the total amount of titanium oxide particles and tungsten oxide particles used. 0.03 parts by mass, platinum was 0.06 parts by mass in terms of atoms), and a photocatalyst dispersion was obtained. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water. The pH was 4.2.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 1.20 h −1 .
（実施例２４）
実施例２１で得たパラジウム及び金含有酸化チタン粒子分散液と、実施例１３で得た白金含有酸化タングステン粒子分散液とを、酸化チタン粒子と酸化タングステン粒子との比率が３：１（質量比）となるように混合して（これにより、分散液中の金、パラジウム及び白金の含有量は、酸化チタン粒子と酸化タングステン粒子との合計使用量１００質量部に対して、金とパラジウムが原子換算で０．０４５質量部、白金が原子換算で０．０３質量部となった）、光触媒体分散液を得た。この光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）を５質量部（固形分濃度５質量％）に水で調整した。ｐＨは５．１であった。
得られた光触媒体分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は１．８９ｈ-1であった。
(Example 24)
The palladium and gold-containing titanium oxide particle dispersion obtained in Example 21 and the platinum-containing tungsten oxide particle dispersion obtained in Example 13 had a ratio of titanium oxide particles to tungsten oxide particles of 3: 1 (mass ratio). (The content of gold, palladium, and platinum in the dispersion is such that the total amount of titanium oxide particles and tungsten oxide particles used is 100 parts by mass with respect to gold and palladium atoms. 0.045 parts by mass in terms of conversion and 0.03 parts by mass of platinum in terms of atoms), and a photocatalyst dispersion. The solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of this photocatalyst dispersion liquid was adjusted to 5 parts by mass (solid content concentration of 5% by mass) with water. The pH was 5.1.
When the obtained photocatalyst dispersion liquid was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order rate constant was 1.89 h −1 .
（実施例２５）
製造例３で得た酸化チタン粒子分散液と製造例４で得た酸化タングステン粒子分散液を、酸化チタン粒子と酸化タングステン粒子との比率が１：１（質量比）となるように混合した。次に、この分散液に、ヘキサクロロ白金酸（Ｈ2ＰｔＣｌ6）水溶液と実施例１５で用いた塩化パラジウム水溶液を、ヘキサクロロ白金酸及び塩化パラジウムが、白金及びパラジウム原子換算で、酸化チタン粒子と酸化タングステン粒子の合計使用量１００質量部に対してそれぞれ０．０４８質量部と０．０１２質量部となるように加えて、ヘキサクロロ白金酸及び塩化パラジウム含有酸化チタン粒子及び酸化タングステン粒子分散液を得た。この分散液に水を加えて、光触媒体分散液１００質量部中に含まれる固形分（酸化チタン粒子と酸化タングステン粒子との合計量）が５質量部（固形分濃度５質量％）となるように水で調整して、酸化チタン粒子及び酸化タングステン粒子分散液を得た。ｐＨは３．８であった。この時点で、得られた分散液を２０℃で３時間保管したところ、保管中に固液分離は見られなかった。また、得られた光触媒体分散液を用いて形成した光触媒体層の光触媒活性（ホルムアルデヒドの分解）を評価したところ、一次反応速度定数は０．８１３ｈ-1であった。
(Example 25)
The titanium oxide particle dispersion obtained in Production Example 3 and the tungsten oxide particle dispersion obtained in Production Example 4 were mixed so that the ratio of titanium oxide particles to tungsten oxide particles was 1: 1 (mass ratio). Next, to this dispersion, hexachloroplatinic acid (H 2 PtCl 6 ) aqueous solution and the palladium chloride aqueous solution used in Example 15 were mixed with hexachloroplatinic acid and palladium chloride in terms of platinum and palladium atoms and oxidized with titanium oxide particles. In addition to 0.048 parts by mass and 0.012 parts by mass with respect to 100 parts by mass of the total amount of tungsten particles used, hexachloroplatinic acid and palladium chloride-containing titanium oxide particles and a tungsten oxide particle dispersion were obtained. . Water is added to this dispersion so that the solid content (total amount of titanium oxide particles and tungsten oxide particles) contained in 100 parts by mass of the photocatalyst dispersion becomes 5 parts by mass (solid content concentration 5% by mass). The mixture was adjusted with water to obtain a titanium oxide particle and tungsten oxide particle dispersion. The pH was 3.8. At this time, when the obtained dispersion was stored at 20 ° C. for 3 hours, no solid-liquid separation was observed during storage. When the photocatalytic activity (decomposition of formaldehyde) of the photocatalyst layer formed using the photocatalyst dispersion liquid was evaluated, the first-order reaction rate constant was 0.813 h −1 .
（参考例１）
実施例１〜２５で得た光触媒体分散液を、それぞれ、天井材に塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、アセトン、トルエン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 1)
Each of the photocatalyst dispersion liquids obtained in Examples 1 to 25 was applied to a ceiling material, and then dried to volatilize the dispersion medium to form a photocatalyst layer on the surface. The concentration of volatile organic substances such as formaldehyde, acetaldehyde, acetone, and toluene in the space and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例２）
実施例１〜２５で得た光触媒体分散液を、それぞれ、タイルに塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 2)
Each of the photocatalyst dispersion liquids obtained in Examples 1 to 25 was applied to a tile, and then dried to volatilize the dispersion medium to form a photocatalyst layer on the surface. The concentration of volatile organic substances such as formaldehyde, acetaldehyde, toluene, and acetone and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例３）
実施例１〜２５で得た光触媒体分散液をそれぞれガラスに塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 3)
Each of the photocatalyst dispersion liquids obtained in Examples 1 to 25 was applied to glass, and then dried to volatilize the dispersion medium to form a photocatalyst layer on the surface. Further, the concentration of volatile organic substances such as acetaldehyde, toluene, and acetone and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例４）
実施例１〜２５で得た光触媒体分散液をそれぞれ壁紙に塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 4)
Each of the photocatalyst dispersion liquids obtained in Examples 1 to 25 was applied to wallpaper, then dried to volatilize the dispersion medium, and a photocatalyst layer was formed on the surface. Further, the concentration of volatile organic substances such as acetaldehyde, toluene, and acetone and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例５）
実施例１〜２５で得た光触媒体分散液をそれぞれ床に塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 5)
When the photocatalyst dispersion liquid obtained in each of Examples 1 to 25 was applied to the floor and then dried to volatilize the dispersion medium to form a photocatalyst layer on the surface, formaldehyde in an indoor space was formed by light irradiation with indoor lighting. Further, the concentration of volatile organic substances such as acetaldehyde, toluene, and acetone and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例６）
実施例１〜２５で得た光触媒体分散液を自動車用インストルメントパネル、自動車用シート、自動車天井材などの自動車内装材の表面に塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、車内照明による光照射により、車内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 6)
The photocatalyst dispersion liquid obtained in Examples 1 to 25 was applied to the surface of an automotive interior material such as an automotive instrument panel, an automotive seat, and an automotive ceiling material, and then dried to volatilize the dispersion medium, When the photocatalyst layer is formed, the concentration of volatile organic substances such as formaldehyde, acetaldehyde, toluene, acetone, and malodorous substances in the interior space can be reduced by light irradiation from the interior lighting. Can kill the pathogens.
（参考例７）
実施例１〜２５で得た光触媒体分散液をそれぞれエアコンの表面に塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明による光照射により、屋内空間におけるホルムアルデヒド、アセトアルデヒド、トルエン、アセトン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 7)
Each of the photocatalyst dispersion liquids obtained in Examples 1 to 25 was applied to the surface of an air conditioner, and then dried to volatilize the dispersion medium to form a photocatalyst layer on the surface. The concentration of volatile organic substances such as formaldehyde, acetaldehyde, toluene, and acetone and the concentration of malodorous substances can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
（参考例８）
実施例１〜２５で得た光触媒体分散液をそれぞれ冷蔵庫に塗布し、その後、乾燥して分散媒を揮発させ、表面に光触媒体層を形成すると、屋内照明や冷蔵庫内の光源による光照射により、冷蔵庫におけるエチレン等の揮発性有機物濃度や悪臭物質の濃度を低減することができ、さらに、黄色ブドウ球菌や大腸菌等の病原菌を死滅させることができる。
(Reference Example 8)
When the photocatalyst dispersion liquid obtained in each of Examples 1 to 25 was applied to a refrigerator and then dried to volatilize the dispersion medium and a photocatalyst layer was formed on the surface, it was irradiated by light from indoor lighting or a light source in the refrigerator. The concentration of volatile organic substances such as ethylene and the concentration of malodorous substances in the refrigerator can be reduced, and pathogenic bacteria such as Staphylococcus aureus and Escherichia coli can be killed.
Claims (10)
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009024051A JP2010115635A (en) | 2008-06-05 | 2009-02-04 | Photocatalyst dispersion, its method of manufacturing the same and application thereof |
| KR1020090049060A KR20090127084A (en) | 2008-06-05 | 2009-06-03 | Photocatalyst dispersion liquid and process for producing the same |
| TW098118564A TW201000208A (en) | 2008-06-05 | 2009-06-04 | Photocatalyst dispersion liquid and process for producing the same |
| AU2009202243A AU2009202243A1 (en) | 2008-06-05 | 2009-06-04 | Photocatalyst dispersion liquid and process for producing the same |
| CA 2668256 CA2668256A1 (en) | 2008-06-05 | 2009-06-04 | Photocatalyst dispersion liquid and process for producing the same |
| US12/478,079 US20090305879A1 (en) | 2008-06-05 | 2009-06-04 | Photocatalyst dispersion liquid and process for producing the same |
| EP09251496A EP2130587A3 (en) | 2008-06-05 | 2009-06-05 | Photocatalyst dispersion liquid and process for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008148404 | 2008-06-05 | ||
| JP2008265422 | 2008-10-14 | ||
| JP2009024051A JP2010115635A (en) | 2008-06-05 | 2009-02-04 | Photocatalyst dispersion, its method of manufacturing the same and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2010115635A true JP2010115635A (en) | 2010-05-27 |
Family
ID=41082574
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009024051A Pending JP2010115635A (en) | 2008-06-05 | 2009-02-04 | Photocatalyst dispersion, its method of manufacturing the same and application thereof |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20090305879A1 (en) |
| EP (1) | EP2130587A3 (en) |
| JP (1) | JP2010115635A (en) |
| KR (1) | KR20090127084A (en) |
| AU (1) | AU2009202243A1 (en) |
| TW (1) | TW201000208A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012045519A (en) * | 2010-08-30 | 2012-03-08 | Sekisui Jushi Co Ltd | Method for manufacturing photocatalyst dispersion, and method for manufacturing photocatalyst |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4730400B2 (en) * | 2007-10-09 | 2011-07-20 | 住友化学株式会社 | Photocatalyst dispersion |
| JP5082950B2 (en) * | 2008-03-13 | 2012-11-28 | 住友化学株式会社 | Method for decomposing volatile aromatic compounds |
| JP2010180303A (en) | 2009-02-04 | 2010-08-19 | Sumitomo Chemical Co Ltd | Hydrophilizing agent, method of producing the same, and use of the same |
| JP4829321B2 (en) * | 2009-03-31 | 2011-12-07 | 株式会社東芝 | Photocatalyst |
| JP2011005475A (en) * | 2009-05-29 | 2011-01-13 | Sumitomo Chemical Co Ltd | Photocatalyst dispersion liquid and photocatalyst functional product using the same |
| WO2014118372A1 (en) | 2013-02-02 | 2014-08-07 | Joma International A/S | An aqueous dispersion comprising tio2 particles |
| CN104525236A (en) * | 2014-12-24 | 2015-04-22 | 陕西科技大学 | Process for preparing nanometer titanium dioxide ternary photocatalyst doped with nitrogen and rare earth elements |
| CN115888846B (en) * | 2023-02-15 | 2024-03-29 | 昆明理工大学 | Composite photocatalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10114545A (en) * | 1996-08-22 | 1998-05-06 | Toto Ltd | Photocatalytic hydrophilic member, its production and photocatalytic hydrophilic coating composition |
| JP2001070800A (en) * | 1999-09-07 | 2001-03-21 | Sharp Corp | Photocatalyst film composition and photocatalyst body using the same |
| JP2005054139A (en) * | 2003-08-07 | 2005-03-03 | Ishihara Sangyo Kaisha Ltd | Coating material to carry photocatalyst and photocatalyst body using the same |
| JP2005144383A (en) * | 2003-11-18 | 2005-06-09 | Koto Seishoku Kk | Photocatalyst-processed sheet |
| JP2006198465A (en) * | 2005-01-18 | 2006-08-03 | Nippon Shokubai Co Ltd | Photocatalyst and its production method |
Family Cites Families (55)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU676299B2 (en) * | 1993-06-28 | 1997-03-06 | Akira Fujishima | Photocatalyst composite and process for producing the same |
| JP2776259B2 (en) | 1994-08-31 | 1998-07-16 | 松下電工株式会社 | Antibacterial inorganic paint |
| JPH08318166A (en) * | 1995-05-25 | 1996-12-03 | Agency Of Ind Science & Technol | Immobilized photocatalyst and method for immobilizing photocatalyst |
| JPH0925437A (en) | 1995-07-12 | 1997-01-28 | Matsushita Electric Works Ltd | Antimicrobial inorganic coating material |
| JP3682506B2 (en) | 1996-10-30 | 2005-08-10 | Ｊｓｒ株式会社 | Coating composition |
| JP3493959B2 (en) | 1996-10-30 | 2004-02-03 | Ｊｓｒ株式会社 | Composition for coating |
| JP3182107B2 (en) * | 1996-12-13 | 2001-07-03 | 松下電工株式会社 | Functional coatings, their production methods and applications |
| JPH10168349A (en) | 1997-12-26 | 1998-06-23 | Matsushita Electric Works Ltd | Antimicrobial inorganic coating |
| KR20010079672A (en) * | 1998-08-21 | 2001-08-22 | 추후제출 | Visible radiation type photocatalyst and production method thereof |
| JP3252136B2 (en) | 1998-08-21 | 2002-01-28 | 有限会社環境デバイス研究所 | Visible light type photocatalyst and method for producing the same |
| DE69930399T2 (en) * | 1998-09-30 | 2006-12-07 | Nippon Sheet Glass Co., Ltd. | PHOTOCATORATORY ITEMS FOR PREVENTING CONSTROGENSES AND DEPOSITS, METHOD FOR PRODUCING THE ARTICLE |
| JP3959213B2 (en) * | 1999-06-30 | 2007-08-15 | 住友化学株式会社 | Titanium oxide, photocatalyst body using the same, and photocatalyst body coating agent |
| EP1205245A4 (en) * | 1999-08-05 | 2005-01-19 | Toyoda Chuo Kenkyusho Kk | Photocatalytic material and photocatalytic article |
| JP2001190953A (en) | 1999-10-29 | 2001-07-17 | Sumitomo Chem Co Ltd | Titanium oxide, photocatalyst body formed by using it, and photocatalyst body coating agent |
| TWI279254B (en) * | 1999-10-29 | 2007-04-21 | Sumitomo Chemical Co | Titanium oxide, and photocatalyst and photocatalyst coating composition using the same |
| JP3959226B2 (en) | 2000-02-24 | 2007-08-15 | 住友化学株式会社 | Photocatalyst body and photocatalyst body coating agent |
| JP4103324B2 (en) | 2000-03-06 | 2008-06-18 | 住友化学株式会社 | Titanium oxide, photocatalyst body and photocatalyst body coating agent using the same |
| JP2001302241A (en) | 2000-04-24 | 2001-10-31 | Sumitomo Chem Co Ltd | Method for producing titanium oxide |
| JP2001354422A (en) | 2000-06-13 | 2001-12-25 | Sumitomo Chem Co Ltd | Method for manufacturing titanium oxide |
| JP2001278626A (en) | 2000-03-31 | 2001-10-10 | Sumitomo Chem Co Ltd | Method of producing titanium oxide |
| JP2001278625A (en) | 2000-03-31 | 2001-10-10 | Sumitomo Chem Co Ltd | Method of producing titanium oxide |
| JP2001278627A (en) | 2000-03-31 | 2001-10-10 | Sumitomo Chem Co Ltd | Method of producing titanium oxide |
| CN1210100C (en) * | 2000-03-31 | 2005-07-13 | 住友化学工业株式会社 | Method for preparing titanium dioxide |
| JP2001335321A (en) * | 2000-05-24 | 2001-12-04 | Sumitomo Chem Co Ltd | Titanium hydroxide, and photocatalyst and coating agent prepared therewith |
| JP2002029750A (en) | 2000-07-12 | 2002-01-29 | Sumitomo Chem Co Ltd | Titanium oxysulfate and method for producing titanium dioxide by using the same |
| JP2002029749A (en) | 2000-07-13 | 2002-01-29 | Sumitomo Chem Co Ltd | Titanium dioxide, photocatalytic body using the same and photocatalytic body coating agent |
| JP3949374B2 (en) | 2000-07-17 | 2007-07-25 | 住友化学株式会社 | Titanium oxide, photocatalyst and photocatalyst coating using the same |
| JP2002047012A (en) | 2000-07-31 | 2002-02-12 | Sumitomo Chem Co Ltd | Method of manufacturing titanium oxide |
| US6726891B2 (en) * | 2000-07-31 | 2004-04-27 | Sumitomo Chemical Company, Limited | Titanium oxide production process |
| JP2002060221A (en) | 2000-08-21 | 2002-02-26 | Sumitomo Chem Co Ltd | Method for producing titanium oxide |
| JP4078479B2 (en) | 2000-12-21 | 2008-04-23 | 住友化学株式会社 | Method for producing titanium oxide |
| JP2002193618A (en) * | 2000-12-25 | 2002-07-10 | Sumitomo Chem Co Ltd | Titanium hydroxide, coating agent using the same, and method of producing titanium oxide |
| US7060643B2 (en) * | 2000-12-28 | 2006-06-13 | Showa Denko Kabushiki Kaisha | Photo-functional powder and applications thereof |
| ATE395134T1 (en) | 2000-12-28 | 2008-05-15 | Showa Denko Kk | HIGHLY ACTIVE PHOTOCATALYST |
| US6887816B2 (en) * | 2000-12-28 | 2005-05-03 | Showa Denko K.K. | Photocatalyst |
| EP1354628B1 (en) * | 2000-12-28 | 2008-05-14 | Showa Denko K.K. | Powder exhibiting optical function and use thereof |
| JP3987289B2 (en) | 2001-02-15 | 2007-10-03 | 石原産業株式会社 | Photocatalyst, method for producing the same, and photocatalyst using the same |
| JP2003013007A (en) * | 2001-06-29 | 2003-01-15 | Nippon Unicar Co Ltd | Coating composition and building material using the same |
| US7378371B2 (en) * | 2001-12-21 | 2008-05-27 | Show A Denko K.K. | Highly active photocatalyst particles, method of production therefor, and use thereof |
| US7414009B2 (en) * | 2001-12-21 | 2008-08-19 | Showa Denko K.K. | Highly active photocatalyst particles, method of production therefor, and use thereof |
| EP1504816A4 (en) * | 2002-03-25 | 2010-11-24 | Osaka Titanium Technologies Co | Titanium oxide photocatalyst, process for producing the same and application |
| JP4199490B2 (en) | 2002-07-26 | 2008-12-17 | パナソニック電工株式会社 | Coating material composition |
| JP2004107381A (en) | 2002-09-13 | 2004-04-08 | Matsushita Electric Works Ltd | Coating material composition and coated product thereof |
| JP4352721B2 (en) | 2003-02-24 | 2009-10-28 | パナソニック電工株式会社 | Functional inorganic paint and its coating composition |
| US7255831B2 (en) * | 2003-05-30 | 2007-08-14 | Carrier Corporation | Tungsten oxide/titanium dioxide photocatalyst for improving indoor air quality |
| JP2004359902A (en) | 2003-06-06 | 2004-12-24 | Matsushita Electric Works Ltd | Photocatalytic coating material |
| JP2005113028A (en) | 2003-10-08 | 2005-04-28 | Jsr Corp | Coating composition and structure |
| JP4507066B2 (en) | 2004-02-18 | 2010-07-21 | 多木化学株式会社 | Tungsten oxide-containing titanium oxide sol, production method thereof, coating agent and optical functional body |
| JP2005230661A (en) | 2004-02-18 | 2005-09-02 | Jsr Corp | Photocatalyst composition for visible light and coating film containing photocatalyst for visible light |
| JP2007069093A (en) | 2005-09-06 | 2007-03-22 | Mitsui Chemicals Inc | Rutile type titanium dioxide ultrafine particle photocatalyst |
| JP5336694B2 (en) | 2005-12-12 | 2013-11-06 | パナソニック株式会社 | Painted |
| JP4783315B2 (en) * | 2006-03-10 | 2011-09-28 | 住友化学株式会社 | Photocatalyst dispersion |
| JP4730400B2 (en) * | 2007-10-09 | 2011-07-20 | 住友化学株式会社 | Photocatalyst dispersion |
| JP5082950B2 (en) * | 2008-03-13 | 2012-11-28 | 住友化学株式会社 | Method for decomposing volatile aromatic compounds |
| JP2010180303A (en) * | 2009-02-04 | 2010-08-19 | Sumitomo Chemical Co Ltd | Hydrophilizing agent, method of producing the same, and use of the same |
-
2009
- 2009-02-04 JP JP2009024051A patent/JP2010115635A/en active Pending
- 2009-06-03 KR KR1020090049060A patent/KR20090127084A/en not_active Application Discontinuation
- 2009-06-04 TW TW098118564A patent/TW201000208A/en unknown
- 2009-06-04 US US12/478,079 patent/US20090305879A1/en not_active Abandoned
- 2009-06-04 AU AU2009202243A patent/AU2009202243A1/en not_active Abandoned
- 2009-06-05 EP EP09251496A patent/EP2130587A3/en not_active Withdrawn
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10114545A (en) * | 1996-08-22 | 1998-05-06 | Toto Ltd | Photocatalytic hydrophilic member, its production and photocatalytic hydrophilic coating composition |
| JP2001070800A (en) * | 1999-09-07 | 2001-03-21 | Sharp Corp | Photocatalyst film composition and photocatalyst body using the same |
| JP2005054139A (en) * | 2003-08-07 | 2005-03-03 | Ishihara Sangyo Kaisha Ltd | Coating material to carry photocatalyst and photocatalyst body using the same |
| JP2005144383A (en) * | 2003-11-18 | 2005-06-09 | Koto Seishoku Kk | Photocatalyst-processed sheet |
| JP2006198465A (en) * | 2005-01-18 | 2006-08-03 | Nippon Shokubai Co Ltd | Photocatalyst and its production method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012045519A (en) * | 2010-08-30 | 2012-03-08 | Sekisui Jushi Co Ltd | Method for manufacturing photocatalyst dispersion, and method for manufacturing photocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| AU2009202243A1 (en) | 2009-12-24 |
| TW201000208A (en) | 2010-01-01 |
| EP2130587A2 (en) | 2009-12-09 |
| EP2130587A3 (en) | 2011-05-11 |
| KR20090127084A (en) | 2009-12-09 |
| US20090305879A1 (en) | 2009-12-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2010115635A (en) | Photocatalyst dispersion, its method of manufacturing the same and application thereof | |
| JP2011005475A (en) | Photocatalyst dispersion liquid and photocatalyst functional product using the same | |
| JP2011036770A (en) | Method for producing noble metal-supported photocatalyst particle | |
| EP2133311B1 (en) | Zirconium oxalate sol | |
| JP2010180303A (en) | Hydrophilizing agent, method of producing the same, and use of the same | |
| US20160332147A1 (en) | Photocatalyst material and method for producing same | |
| CN103079700A (en) | Tungsten oxide photocatalyst and method for producing the same | |
| JP2012110831A (en) | Photocatalyst for decomposing volatile aromatic compound, and product having photocatalytic function | |
| JP2011078930A (en) | Photocatalyst dispersion and photocatalyst functional product using the same | |
| JP2011132626A (en) | Textile product supporting photocatalyst | |
| JP2011020009A (en) | Photocatalyst body for decomposing volatile aromatic compound, and functional product of photocatalyst | |
| JP2011178930A (en) | Photocatalytic coating liquid and article having photocatalytic layer coated with the coating liquid | |
| JP5313051B2 (en) | Zirconium oxalate sol | |
| JP2003190811A (en) | Photocatalytic body, method for manufacturing the same, and photocatalytic body coating agent obtained by using the same | |
| JP4265685B2 (en) | Photocatalyst body, method for producing the same, and photocatalyst body coating agent using the same | |
| JP2010214309A (en) | Photocatalytic body-dispersed liquid and application thereof | |
| CN101596460A (en) | Photocatalyst dispersion liquid and manufacture method thereof | |
| JP2010215781A (en) | Precoating liquid for photocatalyst layer, wallpaper intermediate including photocatalyst layer with precoating liquid applied thereto, and wallpaper including photocatalyst layer | |
| JP5113723B2 (en) | Photocatalyst dispersion | |
| JP2010120805A (en) | Photocatalytic body dispersion | |
| JP5512223B2 (en) | Noble metal-supported photocatalyst particle dispersion and photocatalyst functional product | |
| JP2011050802A (en) | Method for producing dispersion liquid of noble metal-deposited photocatalyst particle | |
| JP2012017238A (en) | Method for producing oxide particle dispersion liquid, oxide particle dispersion liquid, and photocatalyst functional product | |
| JP2010270543A (en) | Product with photocatalytic body layer | |
| CA2668256A1 (en) | Photocatalyst dispersion liquid and process for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20111118 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20121214 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20130122 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130528 |